CN109980167A - Polyvinylidene difluoride film and its preparation and the application for having bionical three periods minimal surface structure - Google Patents

Polyvinylidene difluoride film and its preparation and the application for having bionical three periods minimal surface structure Download PDF

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CN109980167A
CN109980167A CN201910170558.7A CN201910170558A CN109980167A CN 109980167 A CN109980167 A CN 109980167A CN 201910170558 A CN201910170558 A CN 201910170558A CN 109980167 A CN109980167 A CN 109980167A
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sea urchin
urchin shell
pvdf
thin slice
polyvinylidene difluoride
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CN109980167B (en
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刘育京
吴玉选
杨涛
袁华栋
郑建辉
胡华良
孙国元
卢功勋
张文魁
陶新永
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Zhejiang University of Technology ZJUT
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of polyvinylidene difluoride film for having bionical three periods minimal surface structure and its preparations and application.The polyvinylidene fluoride film is using the sea urchin shell with three period minimal surface structures as template, it is prepared by the following: the sea urchin shell thin slice that thickness is no more than 160 μm is made in sea urchin shell, PVDF is penetrated into the skeleton of sea urchin shell thin slice by solvent and is filled up completely the skeleton, the sea urchin shell thin slice acid soak removal sea urchin shell template of PVDF be will be filled with to get to the polyvinylidene difluoride film for having bionical three periods minimal surface structure.When the polyvinylidene difluoride film for having bionical three periods minimal surface structure is used as lithium metal battery diaphragm, the cyclical stability of lithium metal battery can be significantly improved.

Description

Have bionical three periods minimal surface structure polyvinylidene difluoride film and its preparation and Using
(1) technical field
The invention belongs to field of lithium, are related to the polytetrafluoro that one kind has bionical three periods minimal surface (TPMS) structure Vinyl film and its preparation and application as diaphragm in lithium metal battery field.
(2) background technique
Diaphragm material plays very important effect in lithium battery, it prevents positive and negative anodes from contacting between positive and negative anodes, And while non-conductive sub- can freely diversion son.It is active due to lithium metal itself but for lithium metal battery Property, it constantly reacts with organic electrolyte in charge and discharge process, forms SEI, simultaneously because lithium metal charge and discharge process In also can lead to the continuous rupture of SEI along with huge volume change, continuous consumption electrolyte.Since lithium metal is depositing Inhomogeneities in the process can be constantly be generated Li dendrite, and piercing through diaphragm leads to serious safety problem.In order to solve lithium metal The problems of battery obtains the lithium metal battery of higher coulombic efficiency, more excellent chemical property, and there has been proposed various The solution of various kinds, is such as designed collector, uses electrolysis additive or design novel high density electrolyte.But Many people ignore effect of the diaphragm in lithium metal battery.PVDF has chemical resistance, processability and antifatigue and creep properties, Electrical insulating property, these excellent characteristics make PVDF especially extensive in field of lithium application, including binder, diaphragm etc. are multiple Aspect.But traditional PVDF diaphragm material preparation process is complicated, higher cost.To obtain porous PVDF diaphragm material, need PVDF is mixed with inorganic filler, this limits its development to a certain extent, and has for three periods orderly to obtain The diaphragm material of network structure is even more extremely difficult.
On earth, sea urchin, which exists, has more than one hundred million years away from the present, is the low ancient invertebrate in one of ocean.Sea urchin There are many type, there is more than 750 kinds in the world.Sea urchin plate-like or spherical gallbladder shell are hard shell, the quilt generally in sea urchin treatment process As solid waste, but according to records, sea urchin shell can be used to treat asthma, stomach on Chinese medicine not only without toxicity The symptoms such as pain.It is reported that sea urchin shell has three period minimal surface structures (TPMS).The invention is intended to utilize three weeks of sea urchin shell Phase minimal surface structure be template, prepare have the shelly-shaped bionical three periods minimal surface structure of sea urchin PVDF diaphragm, and by its As lithium metal battery diaphragm, it is desirably to obtain the lithium metal battery with excellent chemical property.
(3) summary of the invention
Goal of the invention of the invention is to provide a kind of polyvinylidene difluoride film for having bionical three periods minimal surface structure And preparation method thereof and the application in lithium metal battery, the Kynoar for having bionical three periods minimal surface structure it is thin Film can significantly improve the cyclical stability of lithium metal battery when being used as lithium metal battery diaphragm.
Technical solution of the present invention is specifically described below.
In a first aspect, the present invention provides a kind of polyvinylidene difluoride film for having bionical three periods minimal surface structure, The polyvinylidene fluoride film is obtained by the following method using the sea urchin shell with three period minimal surface structures as template : thickness is made in sea urchin shell and is no more than 160 μm of sea urchin shell thin slice, so that PVDF is penetrated into the bone of sea urchin shell thin slice by solvent In frame and it is filled up completely the skeleton, will be filled with the sea urchin shell thin slice acid soak removal sea urchin shell template of PVDF to get tool is arrived The polyvinylidene difluoride film of standby bionical three periods minimal surface structure.
Preferably, sea urchin shell sheet thickness is 80-160 μm.
Preferably, the solvent be NMP, N dinethylformamide (DMF) or dimethyl acetamide (DMAc), more It is preferred that NMP.
The acid that the immersion uses can be hydrochloric acid, acetic acid etc. can be with the acid of calcium carbonate reaction.
Second aspect, the present invention provides a kind of polyvinylidene difluoride films for having bionical three periods minimal surface structure Preparation method includes the following steps:
(1) take it is relatively flat discard white sea urchin shell, be rinsed with water, remove the organic principle of surface residual；Then Clean sea urchin shell is broken, chooses that relatively flat part is spare, relatively flat part should be made as far as possible to have in break-ing process There is surface area as big as possible, area film as big as possible can be prepared, in this way to improve preparation efficiency；
(2) the sea urchin shell thin slice that thickness is no more than 160 μm is made in the clean white sea urchin shell for choosing step (1)；
(3) the sea urchin shell thin slice that step (2) obtains is laid flat in a reservoir, by PVDF solution drop on sea urchin shell thin slice, Until sea urchin shell thin slice is completely covered by PVDF solution, PVDF is infiltered in sea urchin shell thin slice and sea urchin shell skeleton by solvent at this time It is filled completely by PVDF, then in 40-80 DEG C of dry removal solvent, then the one layer of closely knit PVDF that sea urchin shell surface will be covered on It grinds off completely, obtains the sea urchin shell thin slice filled with PVDF；
(4) the sea urchin shell thin slice that will be filled with PVDF, which is placed in acid, sufficiently impregnates removal sea urchin shell template, then successively uses Distilled water and ethanol washing are to neutrality, then are placed in 40-80 DEG C of baking oven and dry to get to having bionical three periods minimal surface The polyvinylidene difluoride film of structure.
In step (1) of the present invention, the discarded sea urchin shell of white is a kind of calcium carbonate material for being derived from the Nature, conduct The skeleton of sea urchin has three period minimal surface structures.The sea urchin of nature is many kinds of, preferably has bigger burnishing surface Long-pending white cake sea urchin.
In step (2) of the present invention, due to sea urchin shell sheet thickness it is too thin if be easily broken, therefore preferred thickness is 80-160 μm.The sea urchin shell thin slice can be obtained by the method cut or polished.The present invention specifically recommends to obtain sea urchin by polishing Shell thin slice: carrying out sea urchin shell with sand paper to be polishing to required thickness, then successively then is placed in water with supersound washing in ethyl alcohol It is dried to obtain sea urchin shell thin slice in the baking oven of 30-100 DEG C (preferably 60-80 DEG C).Preferably, the sand different with granularity Paper successively polishes to sea urchin shell according to the sequence (such as 400,600,800,1000,1200) of granularity from small to large, and one opens Begin with thicker sand paper grinding efficiency to can be improved, behind be not easy to gall with thinner sand paper, and ratio can be obtained More good-looking pattern.As a further preference, it polishes step are as follows: the sand paper for being first 400 with granularity polishes sea urchin shell to two sides It is smooth, after with granularity be 600 sand paper be polishing to close to required thickness, finally with granularity be 1000 sand paper be polishing to it is required Thickness.
In step (3) of the present invention, the solvent of PVDF solution is preferably NMP, N dinethylformamide (DMF) or dimethyl Acetamide (DMAc), more preferable NMP.The preparation method of the nmp solution of PVDF are as follows: be according to PVDF:NMP mass ratio by PVDF 1:5-15 (preferably 1:8-10) is dissolved in NMP, is stirred continuously under 40-60 DEG C (preferably 50 DEG C), is kept PVDF completely molten Solution exists without any bubble or particle in NMP, obtains the nmp solution of PVDF.
In step (3) of the present invention, preferably with the different sand paper of granularity according to granularity from small to large sequence (such as 400,600, 800, one layer of closely knit PVDF for being covered on sea urchin shell surface is ground off completely 1000,1200 etc.), uses thicker sand at the beginning Grinding efficiency can be improved in paper, behind be not easy to gall with thinner sand paper, and good-looking pattern can be obtained.
In step (4) of the present invention, the acid that the immersion uses can be hydrochloric acid, acetic acid etc. can be with calcium carbonate reaction Acid, preferred concentration are the dilute hydrochloric acid of 0.1-1mol/L, and more preferable dilute hydrochloric acid concentration is 0.4-0.8mol/L；Soaking time is preferably 12-48 hours, more preferably 12-24 hours.
The third aspect, the present invention provides the polyvinylidene fluorides for having the shelly-shaped bionical three periods minimal surface structure of sea urchin Application of the alkene film as the diaphragm of lithium metal battery.
Compared with prior art, the beneficial effects are mainly reflected as follows:
(1) polyvinylidene difluoride film prepared by the present invention, due to its special bionical three periods minimal surface structure, relatively There is high porosity and better mechanical property (such as elasticity modulus and surrender in the fine and close PVDF thin film of other methods preparation Stress etc.), it is used as the diaphragm of lithium metal battery, embodies more superior than traditional dense PVDF diaphragm and commercialization PP diaphragm Cyclical stability.
(2) present invention prepares polyvinylidene difluoride film using template, using natural waste sea urchin shell as template, Cost is largely saved, has the characteristics that waste utilization；And the preparation method is simple and efficient, it can be made to solve While the problem of lithium metal battery, lithium metal battery cost is reduced to a certain degree, thus meeting lithium metal battery performance base Preferably meet new energy lithium metal battery sustainable development in future and commercialized requirement on plinth.
(4) Detailed description of the invention
Fig. 1-1 and Fig. 1-2 is the optics picture of the optical picture of the white sea urchin shell of embodiment 1 and the PVDF diaphragm of preparation.
Fig. 2-1, Fig. 2-2 and Fig. 2-3 are sea urchin shell SEM plan view and the SEM plane of PVDF, sectional view respectively.
Fig. 3-1 and Fig. 3-2 is lithium copper battery of the used PVDF of embodiment 1 as diaphragm and commercialization diaphragm preparation respectively It is 2mA/cm in current density2, 5mA/cm2The coulombic efficiency test loop performance map compared.
Fig. 4-1 and Fig. 4-2 is lithium copper electricity of the used PVDF of embodiment 1 as diaphragm and the preparation of routine PVDF diaphragm respectively Pond is 2mA/cm in current density2, 5mA/cm2The coulombic efficiency test loop performance map compared.
(5) specific implementation method
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is unlimited In this.
Comparative example 1: the preparation of conventional PVDF thin film
PVDF is dissolved in NMP according to mass ratio for 1:10, is stirred continuously at 50 DEG C, is dissolved completely in PVDF In NMP, exist without any bubble or particle.PVDF solution is poured on glass matrix, is scraped with 100 microns of scraper, is formed a film, It is subsequently placed in drying in the baking oven for be placed on 60 DEG C, obtains the PVDF thin film that thickness is about 80 μm.
The PVDF thin film of different-thickness can be obtained by using the scraper of different scales.
Embodiment 1
Choose it is relatively flat discard white sea urchin shell, it is rinsed with a large amount of water, remove surface residual albumen and its His organic principle.Clean sea urchin shell is smashed, makes relatively flat part that there is maximum surface area as far as possible；It is dry by what is obtained Net white sea urchin shell, it is first smooth to two sides with the sand paper that granularity is 400 sea urchin shell of polishing, after be polishing to the sand paper that granularity is 600 Close to 100 μm, then continue to granularity be 1000 sand paper be polishing to translucent (about 100 μm), after by it in water Supersound washing 1h, after supersound washing 0.5h in ethanol, be placed in and be dried to obtain nearly transparent thickness in 80 DEG C of baking oven About 100 μm of sea urchin shell thin slice.
Sea urchin shell thin slice after resulting drying is lain in surface plate, after by PVDF according to mass ratio be 1:10 it is molten Solution is stirred continuously at 50 DEG C in NMP, is dissolved completely in PVDF in NMP, exists without any bubble or particle.Later The nmp solution for dissolving PVDF is dripped on sea urchin shell thin slice, until sea urchin shell thin slice is completely covered by PVDF solution, is placed on 60 DEG C baking oven in remove nmp solvent, obtaining load has the sea urchin shell flake composite material of PVDF；The sea urchin shell thin slice of PVDF is answered Condensation material is successively polished with the sand paper that granularity is 400,600,1000 according to granularity from small to large, until being slightly thinner than sea urchin shell The thickness of thin slice grinds off one layer of closely knit PVDF for being covered on sea urchin shell surface completely, and being placed on concentration is 0.8mol/L's 24 hours removal sea urchin shell templates are impregnated in dilute hydrochloric acid, after successively with distilled water and ethanol washing to neutrality, be placed in and be placed on 60 DEG C baking oven in it is dry, the polyvinylidene difluoride film with three period ordered network structures that thickness is about 80 μm can be obtained.
By the polyvinylidene difluoride film with three period ordered network structures being prepared be used for lithium metal battery every Film.The diaphragm is assembled into lithium metal battery and carries out coulombic efficiency test.Specific installation step is as follows: for Li/Cu half-cell The test of coulombic efficiency first washs the copper sheet cut with dilute hydrochloric acid, is washed afterwards with a large amount of deionized water to neutrality, most Afterwards twice with ethanol wash, it air-dries at room temperature.Using the copper sheet after washing as collector and the PVDF diaphragm cut, 1M is used LiTFSI and 1wt%LiNO3DOL/DME (1:1w/w) as the additive (H in the glove box of argon gas as electrolyte2O < 0.01ppm,O2< 0.01ppm) it is assembled.Compare 80 microns of the commercialized PP diaphragm of group selection and the preparation of comparative example 1 PVDF thin film assembles same above step.
Assembled half-cell is tested on new prestige battery carrier, coulombic efficiency is tested, first in 0.01-1V Voltage range activated with 0.05mA, after plated on copper sheet with certain electric current certain capacity lithium i.e. discharge, later with Certain voltage extracts the lithium of plating, to calculate the coulombic efficiency of half-cell.It as a result, can as shown in Fig. 3-1,3-2,4-1,4-2 The lithium copper battery prepared using finding the PVDF thin film with three period ordered network structures for using embodiment 1 to prepare as diaphragm It is respectively 2mA/cm in current density2, 5mA/cm2Under conditions of, it recycles 700 and 400 times respectively, coulombic efficiency remains to be maintained at 95% or more, performance is considerably beyond commercialization PP diaphragm and routine PVDF diaphragm.
Embodiment 2
Choose it is relatively flat discard white sea urchin shell, it is rinsed with a large amount of water, remove surface residual albumen and its His organic principle.Clean sea urchin shell is smashed, makes relatively flat part that there is maximum surface area as far as possible；It is dry by what is obtained Net white sea urchin shell, it is first smooth to two sides with the sand paper that granularity is 600 sea urchin shell of polishing, after be polishing to the sand paper that granularity is 800 Close to 110 μm, then continue to granularity be 1200 sand paper polish translucent (110 μm), after by it, ultrasound is washed in water Wash 2h, after supersound washing 1h in ethanol, being placed in 60 DEG C of baking oven and being dried to obtain nearly transparent thickness is about 110 μm Sea urchin shell thin slice.
Sea urchin shell thin slice after resulting drying is lain in surface plate, after by PVDF according to mass ratio be 1:15 it is molten Solution is stirred continuously at 55 DEG C in NMP, is dissolved completely in PVDF in NMP, exists without any bubble or particle.Later The nmp solution for dissolving PVDF is dripped on sea urchin shell thin slice, until sea urchin shell thin slice is completely covered by PVDF solution, is placed on 60 DEG C baking oven in remove nmp solvent, obtaining load has the sea urchin shell flake composite material of PVDF；The sea urchin shell thin slice of PVDF is answered Condensation material is successively polished with the sand paper that granularity is 600,800,1200 according to granularity from small to large, until being slightly thinner than sea urchin shell The thickness of thin slice grinds off one layer of closely knit PVDF for being covered on sea urchin shell surface completely, and being placed on concentration is 0.5mol/L's 24 hours removal sea urchin shell templates are impregnated in dilute hydrochloric acid, after successively with distilled water and ethanol washing to neutrality, be placed in and be placed on 60 DEG C baking oven in it is dry, the polyvinylidene difluoride film with a thickness of 100 μm with three period ordered network structures can be obtained.
By the polyvinylidene difluoride film with three period ordered network structures being prepared be used for lithium metal battery every Film.The diaphragm is assembled into lithium metal battery and carries out coulombic efficiency test.Specific installation step is as follows: for Li/Cu half-cell The test of coulombic efficiency first washs the copper sheet cut with dilute hydrochloric acid, is washed afterwards with a large amount of deionized water to neutrality, most Afterwards twice with ethanol wash, it air-dries at room temperature.Using the copper sheet after washing as collector and the PVDF diaphragm cut, 1M is used LiTFSI and 1wt%LiNO3DOL/DME (1:1w/w) as the additive (H in the glove box of argon gas as electrolyte2O < 0.01ppm,O2< 0.01ppm) it is assembled.Compare group selection commercialization polypropylene PP diaphragm and the preparation of comparative example 1 100 are micro- Rice PVDF diaphragm, assembles same above step.
Assembled half-cell is tested on new prestige battery carrier, coulombic efficiency is tested, first in 0.01-1V Voltage range activated with 0.05mA, after plated on copper sheet with certain electric current certain capacity lithium i.e. discharge, later with Certain voltage extracts the lithium of plating, to calculate the coulombic efficiency of half-cell.As a result, it has been found that having three using prepared by embodiment 2 The lithium copper battery coulombic efficiency with higher and preferably follow that the PVDF thin film of period ordered network structure is prepared as diaphragm Ring performance is 3mA/cm in current density2Under conditions of, it recycling 400 times respectively, coulombic efficiency remains to be maintained at 95% or more, Its performance is considerably beyond commercialization PP diaphragm and routine PVDF diaphragm.
Embodiment 3
Choose it is relatively flat discard white sea urchin shell, it is rinsed with a large amount of water, remove surface residual albumen and its His organic principle.Clean sea urchin shell is smashed, makes relatively flat part that there is maximum surface area as far as possible；It is dry by what is obtained Net white sea urchin shell, it is first smooth to two sides with the sand paper that granularity is 400 sea urchin shell of polishing, after be polishing to the sand paper that granularity is 600 Close to 160 μm, then continue to be polished with the sand paper that granularity is 1000, until translucent (about 160 μm), after it is surpassed in water Sound washs 1h, after supersound washing 0.5h in ethanol, be placed in and be dried to obtain nearly transparent thickness about in 80 DEG C of baking oven For 160 μm of sea urchin shell thin slice.
Sea urchin shell thin slice after resulting drying is lain in surface plate, after by PVDF according to mass ratio be 1:5 it is molten Solution is stirred continuously at 50 DEG C in NMP, is dissolved completely in PVDF in NMP, exists without any bubble or particle.Later The nmp solution for dissolving PVDF is dripped on sea urchin shell thin slice, until sea urchin shell thin slice is completely covered by PVDF solution, is placed on 60 DEG C baking oven in remove nmp solvent, obtaining load has the sea urchin shell flake composite material of PVDF；The sea urchin shell thin slice of PVDF is answered Condensation material is successively polished with the sand paper that granularity is 400,600,1000 according to granularity from small to large, until being slightly thinner than sea urchin shell The thickness of thin slice grinds off one layer of closely knit PVDF for being covered on sea urchin shell surface completely, and being placed on concentration is the dilute of 1mol/L 24 hours removal sea urchin shell templates are impregnated in hydrochloric acid, after successively with distilled water and ethanol washing to neutrality, be placed in and be placed on 60 DEG C Baking oven in it is dry, the polyvinylidene difluoride film with a thickness of 150 μm with three period ordered network structures can be obtained.
By the polyvinylidene difluoride film with three period ordered network structures being prepared be used for lithium metal battery every Film.The diaphragm is assembled into lithium metal battery and carries out coulombic efficiency test.Specific installation step is as follows: for Li/Cu half-cell The test of coulombic efficiency first washs the copper sheet cut with dilute hydrochloric acid, is washed afterwards with a large amount of deionized water to neutrality, most Afterwards twice with ethanol wash, it air-dries at room temperature.Using the copper sheet after washing as collector and the PVDF diaphragm cut, 1M is used LiTFSI and 1wt%LiNO3DOL/DME (1:1w/w) as the additive (H in the glove box of argon gas as electrolyte2O < 0.01ppm,O2< 0.01ppm) it is assembled.Compare group selection commercialization polypropylene PP diaphragm and the preparation of comparative example 1 150 are micro- Rice PVDF diaphragm, assembles same above step.
Assembled half-cell is tested on new prestige battery carrier, coulombic efficiency is tested, first in 0.01-1V Voltage range activated with 0.05mA, after plated on copper sheet with certain electric current certain capacity lithium i.e. discharge, later with Certain voltage extracts the lithium of plating, to calculate the coulombic efficiency of half-cell.As a result, it has been found that making prepared with embodiment 3 have three Lithium copper battery coulombic efficiency equally with higher that the PVDF thin film of period ordered network structure is prepared as diaphragm and more preferable Cycle performance, current density be 2mA/cm2Under conditions of, recycle 400 times respectively, coulombic efficiency remain to be maintained at 95% with On, performance is considerably beyond commercialization PP diaphragm and routine PVDF diaphragm.

Claims (10)

1. a kind of polyvinylidene difluoride film for having bionical three periods minimal surface structure, the polyvinylidene fluoride film is to have There is the sea urchin shell of three period minimal surface structures as template, is prepared by the following: thickness is made in sea urchin shell and is no more than 160 μm of sea urchin shell thin slice penetrates into PVDF in the skeleton of sea urchin shell thin slice by solvent and is filled up completely the skeleton, will fill out Sea urchin shell thin slice acid soak removal sea urchin shell template filled with PVDF is to get to having bionical three periods minimal surface structure Polyvinylidene difluoride film.
2. polyvinylidene difluoride film as described in claim 1, it is characterised in that: sea urchin shell sheet thickness is 80-160 μm.
3. polyvinylidene difluoride film as described in claim 1, it is characterised in that: the solvent is NMP, N N- dimethyl methyl Amide or dimethyl acetamide.
4. a kind of preparation side for the polyvinylidene difluoride film for having bionical three periods minimal surface structure such as one of claim 1-3 Method includes the following steps:
(1) take it is relatively flat discard white sea urchin shell, be rinsed with water, remove the organic principle of surface residual；Then it will wash Net sea urchin shell is broken, and chooses that relatively flat part is spare, and relatively flat part should be made to have to the greatest extent in break-ing process as far as possible Possible big surface area；
(2) the sea urchin shell thin slice that thickness is no more than 160 μm is made in the clean white sea urchin shell for choosing step (1)；
(3) the sea urchin shell thin slice that step (2) obtains is laid flat in a reservoir, by PVDF solution drop on sea urchin shell thin slice, until Sea urchin shell thin slice is completely covered by PVDF solution, and PVDF is infiltered in sea urchin shell thin slice by solvent at this time and sea urchin shell skeleton is complete It is filled by PVDF, then removes solvent in 40-80 DEG C of drying, then one layer of closely knit PVDF for being covered on sea urchin shell surface is complete It grinds off, obtains the sea urchin shell thin slice filled with PVDF；
(4) the sea urchin shell thin slice that will be filled with PVDF, which is placed in acid, sufficiently impregnates removal sea urchin shell template, then successively with distillation Water and ethanol washing are to neutrality, then are placed in 40-80 DEG C of baking oven and dry to get to having bionical three periods minimal surface structure Polyvinylidene difluoride film.
5. preparation method as claimed in claim 4, it is characterised in that: in step (1), the white sea urchin shell is with big smooth The white cake sea urchin of area.
6. preparation method as claimed in claim 4, it is characterised in that: in step (2), obtain sea urchin shell thin slice by polishing: Sea urchin shell is carried out with sand paper to be polishing to required thickness, then successively then is placed in 30-100 in water with supersound washing in ethyl alcohol DEG C baking oven in be dried to obtain sea urchin shell thin slice.
7. preparation method as claimed in claim 5, it is characterised in that: in step (2), with the different sand paper of granularity according to granularity Sequence from small to large successively polishes to sea urchin shell.
8. preparation method as claimed in claim 4, it is characterised in that: in step (3), with the different sand paper of granularity according to granularity Sequence from small to large grinds off one layer of closely knit PVDF for being covered on sea urchin shell surface completely.
9. preparation method as claimed in claim 4, it is characterised in that: in step (4), the acid used that impregnates is that concentration is The dilute hydrochloric acid of 0.1-1mol/L, soaking time are 12-48 hours.
10. the polyvinylidene difluoride film for having the shelly-shaped bionical three periods minimal surface structure of sea urchin as described in claim 1 is made For the application of the diaphragm of lithium metal battery.
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CN113860410A (en) * 2021-09-30 2021-12-31 海南大学 Full-angle solar efficient driving water evaporation bionic material and preparation method thereof

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CN103880003A (en) * 2014-04-10 2014-06-25 苏州宇豪纳米材料有限公司 Graphene material prepared from biological calcium carbonate source and application thereof
CN109244318A (en) * 2018-09-03 2019-01-18 中国科学技术大学 The preparation method of porous aragonite structure micron chip, ceramic diaphragm and preparation method thereof

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CN103880003A (en) * 2014-04-10 2014-06-25 苏州宇豪纳米材料有限公司 Graphene material prepared from biological calcium carbonate source and application thereof
CN109244318A (en) * 2018-09-03 2019-01-18 中国科学技术大学 The preparation method of porous aragonite structure micron chip, ceramic diaphragm and preparation method thereof

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* Cited by examiner, † Cited by third party
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CN113860410A (en) * 2021-09-30 2021-12-31 海南大学 Full-angle solar efficient driving water evaporation bionic material and preparation method thereof
CN113860410B (en) * 2021-09-30 2022-06-10 海南大学 Full-angle solar efficient driving water evaporation bionic material and preparation method thereof

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