CN104505484B - A kind of organo-mineral complexing dielectric film, its preparation method and application - Google Patents
A kind of organo-mineral complexing dielectric film, its preparation method and application Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
This application discloses a kind of organo-mineral complexing dielectric film.The dielectric film is the apertured polymeric film containing porous organo-mineral complexing particle；Wherein, porous organo-mineral complexing particle contains porous mineral and thermosetting resin.The dielectric film has abundant pore structure and high porosity, so as to which the ionic conductivity of dielectric film is greatly improved while polymer low-crystallinity is kept.Wherein, liquid-keeping property of the porous inorganic particulate except dielectric film can be improved, strengthen the cycle life of battery core, moreover it is possible to internally form abundant ion channel, the ionic conductivity and electrochemical stability window of dielectric film are further improved, the requirement of high-voltage system application can be reached.
Description
Technical field
The application is related to a kind of dielectric film, its preparation method and application, belongs to battery material field.
Background technology
With becoming increasingly conspicuous the problems such as environmental pollution, energy crisis and shortage of resources, countries in the world are more and more highly heavy
Depending on the development of the correlation techniques such as efficient, cleaning, regenerative resource and electric vehicle.
The development of popularization, electric car recently as portable electric appts, as high capacity power source of new generation lithium from
Sub- battery has obtained great concern.And gel polymer electrolyte lithium-ion battery is due to not only having height ratio capacity, senior engineer
Make voltage, high circulation life-span, memory-less effect and advantages of environment protection, and safety, pliability are good, easy processing, from 1999
Since year is launched, people's extensive concern is caused immediately.Polymer dielectric film needed for battery must have preferable ion
Electrical conductivity, to ensure that battery has relatively low internal resistance；It is also needed to good mechanical properties in actual applications.Therefore, develop
High performance polymer dielectric film turns into an international and domestic study hotspot.
In order to meet client to the higher and higher requirement of battery core energy density, major battery core producer is compacted by improving pole piece
Density, the methods of reducing isolation film thickness filling active material as far as possible more in identical volume, this is allowed for inside battery core
The space for leaving electrolyte for reduces, and the not corresponding reduction of the consumption of electrolyte, so that the liquid that rises occurs in soft pack cell
Problem；And the liquid that rises can influence the problems such as outward appearance and super thick of battery core, battery core shipment is directly affected.In addition, high-energy-density is adjoint
This high-tension application, therefore, exploitation are extremely urgent suitable for the high-performance dielectric film of high voltage system.
The content of the invention
According to the one side of the application, there is provided a kind of Organic-inorganic composite dielectric film.The dielectric film is keeping poly-
While compound low-crystallinity, there is abundant pore structure and high porosity, so as to be greatly improved dielectric film from
Subconductivity rate.Wherein, liquid-keeping property of the porous inorganic particulate except dielectric film can be improved, the cycle life of battery core is strengthened,
Abundant ion channel can also be internally formed, further improves the ionic conductivity and electrochemical stability window of dielectric film,
The requirement of high-voltage system application can be reached.
The Organic-inorganic composite dielectric film, it is characterised in that the Organic-inorganic composite dielectric film be containing
The apertured polymeric film of porous organic-inorganic compound particle；The porous organic-inorganic compound particle contain porous mineral and
Thermosetting resin.
Preferably, the porosity of the Organic-inorganic composite dielectric film is not less than 45%.Preferably, the organic-nothing
The porosity of machine composite electrolyte membrane not less than 48%, 54%, 55%, 56%, 57%, 58%, 60%, 61%, 62%,
63%th, 65%, 68% or 70%.
Preferably, macropore and aperture are contained in the Organic-inorganic composite dielectric film；The average pore size of the macropore is
200~1000nm, the average pore size of the aperture is 30~500nm；The average pore size of macropore is more than the average pore size of aperture.
Preferably, the average pore size scope upper limit of the macropore is selected from 900nm, 800nm, 700nm, 600nm, 560nm, under
Limit is selected from 200nm, 300nm, 400nm, 450nm, 500nm.
Preferably, the average pore size scope upper limit of the aperture is selected from 300nm, 150nm, 100nm, and lower limit is optionally certainly
30nm、40nm、50nm、60nm、70nm、80nm、90nm。
Preferably, the macropore is located at the surface region of dielectric film, and the aperture is located at the inside of dielectric film.
Preferably, the macropore is located at the surface region at least one surface in two surfaces of dielectric film.Further
Preferably, the macropore is located at the surface region on two surfaces of dielectric film.
Preferably, the macropore is located at the region for being no more than Electrolyte film thickness 50% apart from one surface of dielectric film.
That is, when the macropore is located in two surfaces of dielectric film the surface region on surface, the surface region is distance
Dielectric film surface is no more than the region of Electrolyte film thickness 50%.It is further preferred that the macropore is located at apart from electrolyte
One surface of film is no more than the region of Electrolyte film thickness 40%.It is further preferred that the macropore is located at apart from electrolyte
One surface of film is no more than the region of Electrolyte film thickness 30%.
Preferably, the macropore is positioned at the area for being no more than Electrolyte film thickness 25% apart from two surfaces of dielectric film respectively
Domain.That is, when described macropore is located at the surface region on two surfaces of dielectric film, the surface region is apart from dielectric film surface
No more than the region of Electrolyte film thickness 25%.It is further preferred that the macropore is located at respectively apart from two tables of dielectric film
Face is no more than the region of Electrolyte film thickness 20%.It is further preferred that the macropore is located at respectively apart from dielectric film two
Individual surface is no more than the region of Electrolyte film thickness 15%.
Preferably, the particle diameter of the porous organic-inorganic compound particle is 500~2000nm.
Preferably, the porosity of the porous mineral is 50%~95%.It is further preferred that the porous mineral
The porosity ranges upper limit be selected from 94%, 93%, 92%, 90%, the porosity ranges lower limit of the porous mineral is selected from
50%th, 60%, 70%, 80%.
Preferably, the porous mineral is selected from Al2O3、TiO2、SiO2、MgO、ZrO2、AlBr3、BaTiO3In at least
It is a kind of.
Preferably, the porous organic polymer membrane contains Kynoar (being abbreviated as PVDF), Kynoar-hexafluoro
Propylene copolymer (being abbreviated as PVDF-HFP), polyacrylonitrile (being abbreviated as PAN), polyoxyethylene (being abbreviated as PEO), polymethyl
At least one of sour methyl esters (being abbreviated as PMMA).
Preferably, polymerization is obtained in the monomer of the thermosetting resin, and at least one contains aldehyde radical.It is further preferred that
The thermosetting resin is selected from phenolic resin, Lauxite, ketone resin, unsaturated polyester resin, epoxy resin, furans tree
At least one of fat, melamine resin.
Preferably, in the porous organic-inorganic compound particle weight/mass percentage composition of thermosetting resin for 5%~
20%.
Preferably, in the Organic-inorganic composite dielectric film, the quality percentage of porous organic-inorganic compound particle contains
Measure as 4%~30%.It is further preferred that in the Organic-inorganic composite dielectric film, porous organic-inorganic compound particle
Weight/mass percentage composition be 5%~29%.It is further preferred that in the Organic-inorganic composite dielectric film, it is porous it is organic-
The weight/mass percentage composition of inorganic compound particles is 9%~29%.
Preferably, in the Organic-inorganic composite dielectric film, poromeric weight/mass percentage composition be 70%~
96%.It is further preferred that in the Organic-inorganic composite dielectric film, poromeric weight/mass percentage composition is 71%
~95%.It is further preferred that in the Organic-inorganic composite dielectric film, poromeric weight/mass percentage composition is
71%~91%.
According to the another aspect of the application, there is provided the method for preparing the Organic-inorganic composite dielectric film, its feature
It is, including at least following steps：
A) by porous mineral add the solution containing thermosetting resin in, be uniformly dispersed, spray drying obtain it is porous it is organic-
Inorganic compound particles；
B) porous organic-inorganic compound particle, polymeric matrix and pore creating material obtained by step a) are mixed in organic solvent
Close uniformly, obtain gel mixture；
C) gel mixture obtained by step b) is stood to primary membrane and formed, primary membrane is at least one coated in substrate
Surface is with after moisture, vacuum drying removing organic solvent and pore creating material, producing the Organic-inorganic composite dielectric film.
Preferably, the solution containing thermosetting resin is the aqueous solution in step a).
Preferably, thermosetting resin described in step a) in phenolic resin, Lauxite, ketone resin at least one
Kind.
Preferably, the temperature of spray drying is 160~200 DEG C in step a).
Preferably, the mass ratio described in step b) in gel mixture is porous organic-inorganic compound particle:Polymer
Matrix:Pore creating material:Organic solvent=0.5~4:10:0.1~2:20~100.
Preferably, organic solvent described in step b) is selected from DMF (being abbreviated as DMF), N, N- dimethyl
At least one of acetamide (being abbreviated as DMAC), 1-METHYLPYRROLIDONE (being abbreviated as NMP).
Preferably, polymeric matrix described in step b) is Kynoar and/or Kynoar-hexafluoropropene copolymerization
Thing.
Preferably, pore creating material described in step b) is polyethylene glycol (being abbreviated as PEG) and/or PVP
(being abbreviated as PVP).
Primary membrane forms to refer in the step b) stands the semi-solid preparation film that 10min~2h is obtained at room temperature.It is further excellent
Selection of land, primary membrane forms to refer in the step b) stands the semi-solid preparation film that 10min~1h is obtained at room temperature.Further preferably
Ground, primary membrane forms to refer in the step b) stands the semi-solid preparation film that 10min~30min is obtained at room temperature.
At least one surface of primary membrane refers to moisture, one surface of primary membrane and moisture or primary membrane two
Surface is and moisture.
The method of one surface of primary membrane and moisture is non-and the primary membrane surface of substrate contact and moisture.
The method of two surfaces of primary membrane and moisture is, non-with that behind the primary membrane surface of substrate contact and moisture, will come into being
Film turn-over, make another side and moisture not with moisture.
Preferably, described in step b) with moisture at room temperature with 1~6h of moisture.Preferably, step b)
Described in moisture at room temperature with 1~3h of moisture.
Preferably, vacuum drying described in step b) is that 1~6h is dried in vacuo at 60~100 DEG C.Those skilled in the art
Vacuum drying vacuum can be selected according to being actually needed.According to common sense in the field, the vacuum commonly used in vacuum drying
Realize the technical scheme of the application.
Film forming procedure in above-mentioned steps b) may be simply referred to as high humidity-high temperature membrane formation process.The film of preliminarily forming, first connect with steam
Touch, violent phase transfer occurs first for the small water drop induction membrane surface of high density in the environment of high humility, forms macropore；So
Afterwards, it is dried in vacuo at 60~100 DEG C so that the solvent in diaphragm slowly volatilizees with pore creating material, is formed in diaphragm internal layer fine and closely woven
Aperture.
In the application, the existing forms that steam refers to water are solution-air two-phases, and wherein liquid phase can be " mist " shape high dispersive form
In the presence of or a large amount of droplet aggregation.
Those skilled in the art can be according to the thickness for being actually needed selection dielectric film.In theory, use is herein described
The dielectric film that method is prepared, compared with the dielectric film of condition of equivalent thickness in the prior art, at least there is the application institute
The beneficial effect stated.
According to the another aspect of the application, there is provided a kind of lithium ion battery, it is characterised in that have containing any of the above-described
Machine-inorganic composite electrolyte film and/or the Organic-inorganic composite dielectric film being prepared according to any of the above-described method.
Preferably, the lithium ion battery is coiled lithium ion battery or stack type lithium ion battery.
The beneficial effect of herein described technical scheme comprises at least：
(1) dielectric film that the application provides, using high humidity-high temperature method film forming, resulting dielectric film can be formed
The hierarchical porous structure of surface macropore inner aperture.The presence of aperture, solves the problems, such as macropore self discharge serious in battery core.Cause
This, the dielectric film that the application provides is not in the problem of self discharge is big, can actually answered while possessing high liquid-keeping property
For in lithium-ion electric core.
(2) the application provide preparation method, using thermosetting resin embedding porous inorganic particulate formed it is porous it is organic-
Inorganic compound particles, linking between inorganic particle and polymeric matrix can be strengthened, improve the mechanical strength of dielectric film with
Toughness, solves the problem of addition of traditional inorganic particle is excessive to cause dielectric film intensity decreases, fragility increase.
(3) porous inorganic particulate contained in the dielectric film that the application provides has big specific surface area, has stronger
Catalytic action, polymeric matrix can be promoted to develop in the curing process towards the disordered state of low-crystallinity, under disordered state, polymerization
Thing molecule is closely knit with reference to no crystalline state, is advantageous to Li+Transmission, Li can be significantly improved+Transport number.Meanwhile low crystallization
The polymer of degree has higher toughness, can improve the pliability of dielectric film.
(4) hole for having substantial amounts of connectivity inside porous inorganic particulate contained in the dielectric film that the application provides leads to
Road, can largely store electrolyte, increase film body liquid-keeping property, meanwhile, porous particle after this storage electrolyte just as
One Li+The transport hub of transmission, adjust Li+Delivering path in the electrolyte membrane, promotes Li+More efficient transmission is to improve
Ionic conductivity.
(5) porous inorganic particulate contained in the dielectric film that the application provides has intensity suction-operated, can adsorb
Foreign ion and minor amount of water in electrolyte, which grade, adds the stability of film layer and electrode.
Embodiment
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.
In embodiment, DMF is writing a Chinese character in simplified form for DMF；PVDF-HFP is that Kynoar-hexafluoropropene is common
The writing a Chinese character in simplified form of polymers, PEG are the writing a Chinese character in simplified form of polyethylene glycol, the abbreviation that EC is ethylene carbonate；DMC is the writing a Chinese character in simplified form of dimethyl carbonate, PVP
For the writing a Chinese character in simplified form of PVP, EMC is writing a Chinese character in simplified form for methyl ethyl ester.
In implementation column, ionic conductivity is using electrochemical AC impedance method in Shanghai Chen Hua Chi66A type electrochemical operations
Determine, concretely comprise the following steps on standing：Using stainless steel as inert electrode, obstruction electricity is made in the polymer film for soaking electrolyte
Pond, after standing 1h, it is connected on electrochemical workstation, tests open-circuit voltage, open-circuit voltage is arranged to initial voltage, scanning frequency
Rate scope is 100kHz-1Hz, AC amplitude 5mV.
In implementation column, electrochemical stability window uses linear scanning method, in Shanghai Chen Hua Chi66A type electrochemical workstations
Upper measure, is concretely comprised the following steps：First using lithium piece as reference electrode, stainless steel substrates are working electrode, soak the polymer of electrolyte
Film is that simulated battery is made in barrier film, after standing 1h, is connected on electrochemical workstation, tests open-circuit voltage, open-circuit voltage is set
Initial voltage is set to, the response curve by the electric current that linear scan measures with voltage change, sweep speed 5mv/s.
In implementation column, fracture strength Dongguan City Zheng Lan precision instruments Co., Ltd ZL-116 type pulling force aircraft measurements,
Concretely comprise the following steps：Diaphragm is cut into 100*20mm2Rectangle diaphragm, is clipped on puller system, is surveyed with 2mm/min draw speeds
Examination, and records the data of pulling force and displacement, and intensity during fracture is desired value.
In embodiment, porosity and aperture use press pump method in the JW- of precise and tiny Gao Bo science and technology Co., Ltd of Beijing
Determine, concretely comprise the following steps on BK132F high-performance static volumetric method micropore analyzers：Barrier film is washed into the disk of 18mm diameters, surveyed
Membrane thicknesses are tried, places into pressure mercury PORE SIZE APPARATUS FOR and tests porosity and pore-size distribution.
Comparative example 1
By porous Al2O3After the scattered 30min of (porosity 80%) sonic oscillation in solvent DMF, appropriate polymer is weighed
Matrix PVDF-HFP and pore creating material PEG-200 are added in scattered solution, wherein porous organic-inorganic compound particle
: PVDF-HFP: DMF: PEG-200 mass ratio is 1: 10: 40: 0.1.The homogeneous transparent obtained at room temperature after strong stirring 4h
Gel vacuum outgas after 30min standing, film forming is applied on flat board, after primary membrane body is formed, diaphragm is transferred to
1h is dried under 80 DEG C of vacuum, that is, obtains porous Al2O3Modified PVDF-HFP base electrolyte films, thickness are 20 μm.
By the above-mentioned dielectric film of preparation in 1mol/L LiPF6EC-DMC-EMC (volume ratios 1:1:1) solution immersion is lived
After change.Electrochemical AC impedance method is used to measure its room-temperature conductivity as 1.2mS/cm, it is steady that linear scanning method tests its electrochemistry
It is about 5.4V to determine window, measures fracture strength ＞ 9MPa using puller system, porosity ＞ 40% is measured using mercury injection method, average hole
Footpath 600nm.
Embodiment 1
The preparation of porous organic-inorganic compound particle
Lauxite is added in appropriate deionized water, magnetic agitation forms the solution of viscosity, then will be porous
Al2O3(porosity 80%) stirring obtains uniform suspended emulsion, suspension after 160 DEG C of spray drying, produce particle diameter for 500~
2000nm porous organic-inorganic compound particle.In porous organic-inorganic compound particle, the percentage composition of Lauxite is
5wt%.
The preparation of Organic-inorganic composite dielectric film
Porous organic-inorganic compound particle is weighed into appropriate polymerization in solvent DMF after the scattered 30min of sonic oscillation
Thing matrix PVDF-HFP and pore creating material PEG-200 (mean molecule quantity is 200 polyethylene glycol) are added to scattered molten
In liquid, wherein porous organic-inorganic compound particle: PVDF-HFP: DMF: PEG-200 mass ratio is 1: 10: 40: 0.1.In room
The gel of the homogeneous transparent obtained after the lower strong stirring 4h of temperature, the vacuum outgas after 30min is stood apply film forming on flat board,
Be stored at room temperature 30min and form nascent film body, then with moisture, using atomizer to manufacture high humidity environment so that first film surface
Phase transfer with carrying out close point type under water droplets, form substantial amounts of macropore in membrane surface, diaphragm is transferred to 80 DEG C after 1h
Dried under vacuum so that solvent and pore creating material volatilization inside diaphragm, form fine and closely woven small structure, produce organic and inorganic and answer
Dielectric film is closed, thickness is 20 μm.
The activation of dielectric film and parameter
By the above-mentioned dielectric film of preparation in 1mol/L LiPF6EC-DMC-EMC (volume ratios 1:1:1) solution immersion is lived
After change.Electrochemical AC impedance method is used to measure its room-temperature conductivity as 3.5mS/cm.Linear scanning method test shows that it is electrochemical
It is about 5.5V to learn stability window.Fracture strength ＞ 12MPa are measured using puller system.Porosity ＞ 60% is measured using mercury injection method,
Outer layer average pore size 500nm, internal layer average pore size 30nm, outer layer macropore be distributed in dielectric film surface and dielectric film surface with
Interior thickness is 10 μm of region.
Embodiment 2
The preparation of porous organic-inorganic compound particle
Preparation process is with embodiment 1, and difference is, used porous Al2O3Porosity is 50%.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.5mS/cm.Its electrochemistry is tested using linear scanning method
Stability window ＞ 5.4V.Fracture strength ＞ 12MPa are measured using puller system, porosity ＞ 48%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 50nm.
Embodiment 3
The preparation of porous organic-inorganic compound particle
Preparation process is with embodiment 1, and difference is, used porous Al2O3Porosity is 95%.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 4.6mS/cm.Its electrochemistry is tested using linear scanning method
Stability window ＞ 5.6V.Fracture strength ＞ 15MPa are measured using puller system.Porosity ＞ 65%, outer layer are measured using mercury injection method
Average pore size 600nm, internal layer average pore size 80nm.
Embodiment 4
The preparation of porous organic-inorganic compound particle
Preparation process is with embodiment 1, and difference is, used porous inorganic particulate is that porosity is 80%
SnO2。
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.0mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 15MPa are measured using puller system.Porosity ＞ 56%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 40nm.
Embodiment 5
The preparation of porous organic-inorganic compound particle
Preparation process is with embodiment 1, and difference is, used porous inorganic particulate is that porosity is 80%
TiO2。
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 10MPa are measured using puller system.Porosity ＞ 62%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 50nm.
Embodiment 6
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 0.5: 10: 40: 0.1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.5mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 10MPa are measured using puller system.Porosity ＞ 55%, outer layer are measured using mercury injection method
Average pore size 400nm, internal layer average pore size 30nm.
Embodiment 7
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 4: 10: 40: 0.1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 5.0mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V, fracture strength ＞ 8MPa are measured using puller system, porosity ＞ 68% are measured using mercury injection method, outer layer is put down
Equal aperture 500nm, internal layer average pore size 80nm.
Embodiment 8
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 7.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 7, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 1: 10: 40: 0.5.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.7mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 8MPa are measured using puller system.Porosity ＞ 62% is measured using mercury injection method, outer layer is put down
Equal aperture 800nm, internal layer average pore size 60nm.
Embodiment 9
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 1: 10: 40: 2.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 5.8mS/cm.Linear scanning method, which is tested, to be shown, PVDF-
HFP/Al2O3The electrochemical stability window ＞ 5.2V of electrolytic thin-membrane, fracture strength ＞ 3MPa are measured using puller system, using pressure
Mercury method measures porosity ＞ 70%, outer layer average pore size 1000nm, internal layer average pore size 500nm.
Embodiment 10
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
With embodiment 1, difference is, changes polymer P VDF-HFP into PVDF for preparation process and raw material proportioning.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 1.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.7V.Fracture strength ＞ 25MPa are measured using puller system.Porosity ＞ 48%, outer layer are measured using mercury injection method
Average pore size 200nm, internal layer average pore size 30nm.
Embodiment 11
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
With embodiment 1, difference is, changes polymer P VDF-HFP into PVDF-HFP for preparation process and raw material proportioning
(two kinds of substrate quality ratios are 1 to+PVDF:1).
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.2mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 15MPa are measured using puller system.Porosity ＞ 58%, outer layer are measured using mercury injection method
Average pore size 400nm, internal layer average pore size 40nm.
Embodiment 12
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 1: 10: 100: 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.2mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 57%, outer layer are measured using mercury injection method
Average pore size 800nm, internal layer average pore size 100nm.
Embodiment 13
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF:
PEG-200 mass ratio is 1: 10: 20: 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.5mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 54%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 40nm.
Embodiment 14
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, porous organic-inorganic compound particle: PVDF-HFP: DMF: PVP
Mass ratio be 1: 10: 20: 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.4mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 11MPa are measured using puller system.Porosity ＞ 58%, outer layer are measured using mercury injection method
Average pore size 450nm, internal layer average pore size 60nm.
Embodiment 15
The preparation of porous organic-inorganic compound particle
Preparation process, raw material are with embodiment 1, and difference is, Lauxite in porous organic-inorganic compound particle
Weight/mass percentage composition is 20%.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.7mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 18MPa are measured using puller system.Porosity ＞ 61%, outer layer are measured using mercury injection method
Average pore size 560nm, internal layer average pore size 80nm.
Embodiment 16
The preparation of porous organic-inorganic compound particle
Preparation process, raw material are with embodiment 1, and difference is, Lauxite in porous organic-inorganic compound particle
Weight/mass percentage composition is 10%.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.6mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 15MPa are measured using puller system.Porosity ＞ 62%, outer layer are measured using mercury injection method
Average pore size 600nm, internal layer average pore size 70nm.
Embodiment 17
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are with embodiment 1, and difference is, the temperature of spray drying is 200 DEG C.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.4mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 57%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 60nm.
Embodiment 18
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, the mixing time of solution is 1h.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.5mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 60%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm.
Embodiment 19
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, the time with moisture is 3h, and vacuum drying temperature is
60 DEG C, drying time 6h.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 3.9mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 10MPa are measured using puller system.Porosity ＞ 63%, outer layer are measured using mercury injection method
Average pore size 900nm, internal layer average pore size 150nm.
Embodiment 20
The preparation of porous organic-inorganic compound particle
Preparation process, raw material and proportioning are the same as embodiment 1.
The preparation of Organic-inorganic composite dielectric film
Preparation process is with embodiment 1, and difference is, the time with moisture is 6h, and vacuum drying temperature is
100 DEG C, drying time 1h.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 4.1mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 8MPa are measured using puller system.Porosity ＞ 65% is measured using mercury injection method, outer layer is put down
Equal aperture 1000nm, internal layer average pore size 300nm.
Embodiment 21
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into phenolic resin for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.4mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm.
Embodiment 22
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into ketone resin for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.4mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 46%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 50nm.It is real
Embodiment 23
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into unsaturated polyester resin for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.5mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 47%, outer layer are measured using mercury injection method
Average pore size 300nm, internal layer average pore size 30nm.
Embodiment 24
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into phenolic group propane side-chains type for preparation process, raw material proportioning
Epoxy resin.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.6mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.5V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 45%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm.
Embodiment 25
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into high furfuryl alcohol resin for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.4mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.3V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 44%, outer layer are measured using mercury injection method
Average pore size 700nm, internal layer average pore size 90nm.
Embodiment 26
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into melamino-formaldehyde tree for preparation process, raw material proportioning
Fat.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.3V.Fracture strength ＞ 13MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 300nm, internal layer average pore size 30nm.
Embodiment 27
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes Lauxite into acrylic acid epoxy ester type for preparation process, raw material proportioning
Polyester resin.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 14MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 800nm, internal layer average pore size 100nm.
Embodiment 28
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes the time for forming primary membrane into 10min for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 14MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm.
Embodiment 29
The preparation of porous organic-inorganic compound particle
With embodiment 1, difference is, changes the time for forming primary membrane into 2h for preparation process, raw material proportioning.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 14MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm.
Embodiment 30
The preparation of porous organic-inorganic compound particle
Preparation process, raw material proportioning are with embodiment 1, and difference is during high humidity, after upper surface forms macropore, also
Need to turn on diaphragm, high humidity treatment is done to lower surface, form the eurypyloue polymer film in double surfaces.
The preparation of Organic-inorganic composite dielectric film
Preparation process and material rate are the same as embodiment 1.
The activation of dielectric film and parameter
The activation step of dielectric film is the same as embodiment 1.
AC impedance method is used to test its ionic conductivity as 2.8mS/cm.Linear scanning method test shows its electrochemistry
Stability window ＞ 5.4V.Fracture strength ＞ 14MPa are measured using puller system.Porosity ＞ 49%, outer layer are measured using mercury injection method
Average pore size 500nm, internal layer average pore size 30nm, outer layer macropore be distributed in dielectric film two surfaces and dielectric film it is each
Thickness is 5 μm of region within surface.
The ionic conductivity of above example and comparative example, electrochemical stability window, fracture strength, the test of porosity
Journey parameter setting is just the same.Next the performance test results of Organic-inorganic composite dielectric film are analyzed.
As can be seen that adding porous organic and inorganic from the contrast of embodiment 1 and comparative example (not adding any additive)
Composite particles, the ionic conductivity and porosity of the Organic-inorganic composite dielectric film of preparation are obviously improved, and machinery is strong
Degree has also been lifted with electrochemical stability window, has fully demonstrated relatively conventional of porous organic-inorganic compound particle here
The advantage of grain, first, the hole of porous inorganic particulate in itself can store electrolyte, and form abundant ion channel, improve
Ionic conductivity, going up for porosity is embodied directly in, in addition, the porous inorganic particulate of high-specific surface area can promote polymer
Matrix material converts towards low crystalline state, and the no crystalline polymer of combination between the polymer molecule of this low crystalline state is tight like that
Close, this is advantageous to lift the ability that polymer transmits Li+ in itself, so as to further improve ionic conductivity, in addition, low crystalline state
Party thing there is good toughness, mechanical strength is good, and process is not easy crack or phenomenon of rupture occur.
As can be seen that the porosity lifting of porous inorganic particulate can effectively lift polymer from embodiment 1-3 contrasts
Dielectric film entirety porosity, and the elevator belt of porosity come be ionic conductivity lifting, meanwhile, high porosity is inorganic
Particle also has slight improvement to electrochemical stability window；, it can be seen that improving porous, inorganic from the contrast of embodiment 1,6,7
When the ratio of grain also can effectively improve the porosity but porous inorganic particulate too high levels of polymer dielectric film, it can reduce
The mechanical strength of dielectric film.Ureaformaldehyde in porous organic-inorganic compound particle is can be seen that from the contrast of embodiment 1,14,15
The increase of amount of resin can reduce too high inorganic particle filled the problem of bringing diaphragm mechanical strength to decline, this master to a certain extent
If the link strength between inorganic particle and the Link Ratio polymer of polymer two-phase itself is poor, by spray drying process by urea
Urea formaldehyde is solidificated on porous inorganic particulate, can strengthen the compatibility between inorganic particle and polymeric matrix material, is improved inorganic
Phase and the bond strength of organic alternate contact surface.
It can be seen that improvement effect of the different inorganic particles to hole electrochemical stability window from the contrast of embodiment 1,4,5
Fruit is different, and at this moment the dielectric property of inorganic particle in itself determines, but generally speaking, addition inorganic particle is for electrification
It is favourable to learn stability window.
As can be seen that PVDF matrixes are bigger than the mechanical strength of PVDF-HFP matrix from the contrast of embodiment 1,10,11, but from
Electron conductivity is low, and mechanical strength is that PVDF has a characteristic in itself greatly, and crystallinity height causes low main of PVDF ionic conductivities
Reason, therefore, can be by PVDF and PVDF-HFP come balancing machine intensity and ionic conductivity.
As can be seen that improving the dosage of pore creating material from the contrast of embodiment 1,8,9, polymer electrolytic can be effectively improved
The porosity of plasma membrane, so as to improve ionic conductivity, but the excessive addition of pore creating material can seriously reduce polymer dielectric film
Mechanical strength, the serious processing characteristics for reducing polymer dielectric film.
As can be seen that extending the time of contact with steam from the contrast of embodiment 1,19,20, polymer electrolytic can be improved
The porosity and ionic conductivity of plasma membrane, but the mechanical performance of diaphragm is lost, and this is due to that high humidity time lengthening can increase
The diaphragm depth that the quantity and macropore of membrane surface macropore are related to, so as to improve porosity, but macropore increase, matrix section are actual
Area can reduce, so as to cause mechanical strength to decline.In summary：First, porous inorganic particulate addition (including porosity with
Dosage) porosity of polymer dielectric film can be significantly improved, meanwhile, the crystallinity of polymer is reduced, improves Li+In polymer
In transfer ability, improve the ionic conductivity of polymer dielectric film, secondly, the addition of porous inorganic particulate can improve poly-
The dielectric properties of polymer electrolyte membrane, so as to improve electrochemical stability window to a certain extent, finally, at inorganic particle surfaces
The binding ability of inorganic particle and matrix polymer can substantially be strengthened by managing heat cured Lauxite, improve porous inorganic particulate
The mechanical strength of modified dielectric film.
It is not for limiting claim, any this area skill although the application is disclosed as above with preferred embodiment
Art personnel can make some possible variations and modification on the premise of the application design is not departed from, therefore the application
Protection domain should be defined by the scope that the application claim is defined.
Claims (11)
1. a kind of Organic-inorganic composite dielectric film, it is characterised in that the Organic-inorganic composite dielectric film is containing more
The apertured polymeric film of hole organic-inorganic compound particle；
The porous organic-inorganic compound particle contains porous mineral and thermosetting resin；
The porous organic-inorganic compound particle embeds the porous inorganic particulate by the thermosetting resin and formed；
The porosity of the porous mineral is 50%~95%；
The particle diameter of the porous organic-inorganic compound particle is 500~2000nm.
2. Organic-inorganic composite dielectric film according to claim 1, it is characterised in that the Organic-inorganic composite electricity
Contain macropore and aperture in solution plasma membrane；The average pore size of the macropore is 200~1000nm, and the average pore size of the aperture is 30
~500nm；The average pore size of macropore is more than the average pore size of aperture.
3. Organic-inorganic composite dielectric film according to claim 2, it is characterised in that the macropore is located at electrolyte
The surface region at least one surface in two surfaces of film.
4. Organic-inorganic composite dielectric film according to claim 3, it is characterised in that the macropore is located at electrolyte
The surface region on two surfaces of film.
5. Organic-inorganic composite dielectric film according to claim 2, it is characterised in that the macropore is located at distance electricity
Solve the region that one surface of plasma membrane is no more than Electrolyte film thickness 50%；Or the macropore is located at respectively apart from dielectric film two
Individual surface is no more than the region of Electrolyte film thickness 25%.
6. Organic-inorganic composite dielectric film according to claim 1, it is characterised in that the porous organic and inorganic is answered
The weight/mass percentage composition for closing thermosetting resin in particle is 5%~20%.
7. prepare the method for Organic-inorganic composite dielectric film described in claim 1, it is characterised in that including at least following step
Suddenly：
A) porous mineral is added in the solution containing thermosetting resin, be uniformly dispersed, spray drying obtains porous organic and inorganic
Composite particles；
B) porous organic-inorganic compound particle, polymeric matrix and pore creating material obtained by step a) are mixed in organic solvent
It is even, obtain gel mixture；
C) by gel mixture obtained by step b) coated in substrate, standing 10min~2h obtains primary membrane, by primary membrane extremely
A few surface is with after moisture, vacuum drying removing organic solvent and pore creating material, producing the Organic-inorganic composite electrolysis
Plasma membrane.
8. according to the method for claim 7, it is characterised in that the temperature of spray drying is 160~200 DEG C in step a).
9. according to the method for claim 7, it is characterised in that the mass ratio described in step b) in gel mixture is more
Hole organic-inorganic compound particle:Polymeric matrix:Pore creating material:Organic solvent=0.5~4:10:0.1~2:20~100.
10. according to the method for claim 7, it is characterised in that described in step b) with moisture at room temperature with
1~6h of moisture；The vacuum drying is that 1~6h is dried in vacuo at 60~100 DEG C.
11. a kind of lithium ion battery, it is characterised in that contain the Organic-inorganic composite electricity described in any one of claim 1~6
Solution plasma membrane and/or the Organic-inorganic composite dielectric film being prepared according to any one of claim 7~10 methods described.
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| CN107591561A (en) * | 2017-08-03 | 2018-01-16 | 电子科技大学 | A kind of preparation method of lithium ion battery gel polymer electrolyte |
| CN110416600B (en) * | 2018-04-28 | 2020-12-18 | 上海汽车集团股份有限公司 | Polymer electrolyte membrane and solid-state battery |
| CN109346648B (en) * | 2018-10-15 | 2021-11-02 | 苏州清陶新能源科技有限公司 | Flame-retardant gel ceramic diaphragm and preparation method thereof |
| CN111834591B (en) * | 2019-04-18 | 2022-04-15 | 比亚迪股份有限公司 | Porous diaphragm, preparation method thereof and lithium ion battery |
| CN114122623B (en) * | 2020-08-31 | 2024-11-15 | 青岛蓝科途膜材料有限公司 | A lithium ion battery separator, preparation method and application thereof |
| CN112920430B (en) * | 2021-01-21 | 2022-12-27 | 河北金力新能源科技股份有限公司 | Multi-layer coated inorganic particle, preparation method thereof, aqueous functional coating slurry, lithium battery separator, and lithium battery |
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