CN109065802A - Battery composite diaphragm, lithium ion battery and preparation method - Google Patents
Battery composite diaphragm, lithium ion battery and preparation method Download PDFInfo
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- CN109065802A CN109065802A CN201810761013.9A CN201810761013A CN109065802A CN 109065802 A CN109065802 A CN 109065802A CN 201810761013 A CN201810761013 A CN 201810761013A CN 109065802 A CN109065802 A CN 109065802A
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- 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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Abstract
It includes: to mix nano inorganic powder with diluent that the present invention, which provides a kind of battery composite diaphragm, lithium ion battery and preparation method, the preparation of battery composite diaphragm, obtains a mixed liquor；Polyolefin powder is mixed to mixed liquor and is carried out mixing plasticizing, to form a homogeneous melt；Cooling treatment is carried out to homogeneous melt and forms slab film, stretch processing is carried out to slab film；Diluent is removed, and carries out shaping winding processing, to obtain battery composite diaphragm.Nanometer-level inorganic powder is added in polyalkene diaphragm by the present invention by in-situ blending method, and nano inorganic powder has high thermal stability, can reduce the thermal contraction after lithium battery diaphragm is heated；Nano inorganic powder has biggish specific surface area, and surface has polar functional group, can improve the lyophily performance between polyalkene diaphragm and electrolyte；Nano inorganic powder plays heterogeneous nucleating effect in system, can increase the crystallinity of polyolefin in polyolefin forming process, improves the mechanical strength of diaphragm.
Description
Technical field
The invention belongs to battery diaphragm preparations, more particularly to a kind of battery composite diaphragm, lithium ion battery and preparation side
Method.
Background technique
Lithium ion battery is made of positive electrode, negative electrode material, electrolyte, the big critical material of diaphragm four, wherein diaphragm institute
Play the role of be: isolation positive and negative pole material, prevent internal short-circuit of battery；Diaphragm must have porous structure, can possess
A large amount of electrolyte guarantees that lithium ion quickly conducts inside diaphragm.
Currently, the diaphragm material of commercial applications is mainly polyethylene and polypropylene material, the method for machine-shaping includes
Wet forming and dry-press process.However, there is lacking for following aspect in battery applications in the polyalkene diaphragm material of one-component
Fall into: polyolefin is a kind of polymer that heat resistance is poor, and the stretching in forming process by larger multiplying power, internal stress is high,
When macro manifestations are battery temperature exception, diaphragm is easily heat-shrinked；In addition, polyolefin is a kind of typical apolar polymeric
Object, it is larger with polar electrolyte small molecule polarity spectrum, it is therefore, weak with electrolyte small molecular phase interaction, it is unfavorable for protecting
There are a large amount of electrolyte, part " scarce liquid " is easy to produce in long-time cyclic process, largely effects on the performance of battery.And it leads at present
To apply two methods by ceramics and heat-resistant polymer improves the defect of polyalkene diaphragm, but polyalkene diaphragm surface energy
It is low, have the defects that between ceramics and polymer coating and matrix easily peelable.
Therefore, how a kind of battery composite diaphragm, lithium ion battery and preparation method, it is in the prior art above-mentioned to solve
Problem is necessary.
Summary of the invention
In view of the foregoing deficiencies of prior art, it the purpose of the present invention is to provide a kind of battery composite diaphragm, is used for
Solve the problems such as polyalkene diaphragm temperature tolerance is poor in the prior art, lyophily is poor.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation method of battery composite diaphragm, packet
Include following steps:
1) nano inorganic powder is provided, and the nano inorganic powder is mixed with diluent, obtains a mixed liquor；
2) polyolefin powder is provided, the polyolefin powder is mixed with the mixed liquor and carries out mixing plasticizing, with shape
At a homogeneous melt；
3) cooling treatment is carried out to form a slab film to the homogeneous melt, and the slab film is carried out at stretching
Reason；And
4) diluent in the obtained structure of step 3) is removed, and the structure after the removal diluent is carried out
Winding of being formed is handled, to obtain the battery composite diaphragm.
As a preferred solution of the present invention, it further comprises the steps of: between step 1) and step 2) and is obtained in step 1)
The mixed liquor carry out ball-milling treatment；The time of the ball-milling treatment is carried out between 10min-25min.
As a preferred solution of the present invention, in step 1), the nano inorganic powder includes Al2O3、SiO2、TiO2、
ZrO2, one of MgO, CaO and SiC or a variety of combinations；The partial size of the nano inorganic powder is between 20nm-1000nm
Between.
As a preferred solution of the present invention, in step 1), the diluent includes atoleine, mineral oil, soybean
One of oil, diphenyl ether, dimethylbenzene and toluene or a variety of combinations.
As a preferred solution of the present invention, in step 2), the polyolefin powder is mixed to get with the mixed liquor
Solution in, the mass fraction of the polyolefin powder between 20wt%-35wt%, the diluent mass fraction between
Between 65wt%-80wt%, the mass fraction of the mass fraction of the nano inorganic powder between the polyolefin powder
Between 0.1%-5%.
As a preferred solution of the present invention, in step 2), carrying out the technique for being kneaded plasticizing includes: that described will gather
Alkene powder and the mixed liquor are added in extruder according to the proportion, are sufficiently kneaded plasticizing and are formed the homogeneous melt, wherein
In the extrusion plasticizing temperature in the extruder between 170 DEG C -230 DEG C.
As a preferred solution of the present invention, in step 2), the polyolefin powder includes polyethylene and polypropylene
At least one of, the inherent viscosity of the polyolefin powder between 4.0dl/g-8.0dl/g, the polyolefin powder
Partial size is between 100 μm -300 μm.
As a preferred solution of the present invention, in step 3), the cooling treatment is carried out using Quench roller arrangement and is formed
The slab film, during forming the slab film, the set temperature of the sharp cooling roll is between 10 DEG C -40 DEG C, institute
The movement velocity of slab film is stated between 2m/min-8m/min.
As a preferred solution of the present invention, in step 3), the technique for carrying out the stretch processing includes cross directional stretch
And at least one of longitudinal stretching, wherein the stretching ratio stretching in the transverse direction is between 5-13 times, transverse drawing temperature
Between 110 DEG C -125 DEG C；The stretching ratio of the longitudinal stretching is between 3-10 times, and longitudinal drawing temperature is between 100
Between DEG C -120 DEG C.
As a preferred solution of the present invention, in step 4), remove the diluent includes extraction process, wherein
For the extraction temperature of the extraction process between 20 DEG C -45 DEG C, the extractant of the extraction process includes methylene chloride, ring
One of hexane, dehydrated alcohol and acetone or a variety of combinations；The sizing is carried out to the structure after the removal diluent
The setting temperature of processing is wound between 125 DEG C -135 DEG C.
The present invention also provides a kind of battery composite diaphragm, the raw material for preparing of the battery composite diaphragm includes nano inorganic powder
Body, polyolefin powder and diluent, wherein the battery composite diaphragm is based on the nano inorganic powder, the polyolefin powder
Body is kneaded the homogeneous melt that plasticizing is formed with the diluent and obtains.
As a preferred solution of the present invention, according to parts by weight, in the nano inorganic powder, the polyolefin powder
In the solution that body and the diluent are mixed to get, the mass fraction of the polyolefin powder is between 20wt%-35wt%
Between, the diluent mass fraction is between 65wt%-80wt%, and the mass fraction of the nano inorganic powder is between institute
Between the 0.1%-5% for stating the mass fraction of polyolefin powder.
As a preferred solution of the present invention, the nano inorganic powder includes Al2O3、SiO2、TiO2、ZrO2、MgO、
One of CaO and SiC or a variety of combinations, the partial size of the nano inorganic powder is between 20nm-1000nm；It is described dilute
Releasing agent includes one of atoleine, mineral oil, soybean oil, diphenyl ether, diformazan benzene and toluene or a variety of combinations；It is described poly-
Alkene powder includes at least one of polyethylene and polypropylene, and the inherent viscosity of the polyolefin powder is between 4.0dl/g-
Between 8.0dl/g, the partial size of the polyolefin powder is between 100 μm -300 μm.
The present invention also provides a kind of lithium ion battery, the lithium ion battery includes such as any one of above scheme scheme
The battery composite diaphragm.
As described above, battery composite diaphragm, lithium ion battery and preparation method of the invention, have the advantages that
In battery composite diaphragm provided by the invention and preparation method, nanometer-level inorganic powder is added to by in-situ blending method poly-
In alkene diaphragm, nano inorganic powder has high thermal stability, can substantially reduce the thermal contraction after lithium battery diaphragm is heated；It receives
Rice inorganic particle has biggish specific surface area, and surface has polar functional group, can improve polyalkene diaphragm and electrolyte it
Between lyophily performance；Nano inorganic powder plays heterogeneous nucleating effect in system, can increase in polyolefin forming process poly-
The crystallinity of alkene improves the mechanical strength of diaphragm.
Detailed description of the invention
Fig. 1 is shown as battery composite diaphragm preparation technology flow chart provided by the invention.
Component label instructions
S1~S4 step 1) is to step 4)
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to Fig. 1.It should be noted that illustrating what only the invention is illustrated in a schematic way provided in the present embodiment
Basic conception, though only show in diagram with related component in the present invention rather than component count, shape when according to actual implementation
And size is drawn, when actual implementation form, quantity and the ratio of each component can arbitrarily change for one kind, and its assembly layout
Form may also be increasingly complex.
As shown in Figure 1, the present invention provides a kind of preparation method of battery composite diaphragm, include the following steps:
1) nano inorganic powder is provided, and the nano inorganic powder is mixed with diluent, obtains a mixed liquor；
2) polyolefin powder is provided, the polyolefin powder is mixed with the mixed liquor and carried out mixing plasticizing,
To form a homogeneous melt；
3) cooling treatment is carried out to form a slab film to the homogeneous melt, and the slab film is carried out at stretching
Reason；
4) diluent in the obtained structure of step 3) is removed, and the structure after the removal diluent is carried out
Winding of being formed is handled, to obtain the battery composite diaphragm.
Below in conjunction with the preparation process for the battery composite diaphragm that the present invention will be described in detail.
Firstly, carry out step 1) shown in S1 as shown in figure 1, nano inorganic powder is provided, and by the nano inorganic powder
It is mixed with diluent, obtains a mixed liquor.
As an example, the nano inorganic powder includes Al in step 1)2O3、SiO2、TiO2、ZrO2, MgO, CaO and
One of SiC or a variety of combinations.
As an example, the partial size of the nano inorganic powder is between 20nm-1000nm.
As an example, the diluent includes atoleine, mineral oil, soybean oil, diphenyl ether, dimethylbenzene in step 1)
And one of toluene or a variety of combinations.
Specifically, the diaphragm that the present invention provides a kind of organic/inorganic composite material formation will be received first in this step
Rice inorganic particle and diluent carry out being mixed to get a mixed liquor, wherein the partial size of the nano inorganic powder is preferably between
Between 50nm-200nm.In addition, herein " between ... between " refer to the numberical range extremely including two endpoints.
The mixed liquor obtained in step 1) is carried out as an example, being further comprised the steps of: between step 1) and step 2)
Ball-milling treatment；As an example, carrying out the time of the ball-milling treatment between 10min-25min.
Specifically, in one preferably example, the technique that ball-milling treatment is also carried out to the mixed liquor that step 1) obtains,
Preliminary mixed liquor obtains more uniform mixed liquor after ball milling, the time of ball-milling treatment be preferably between 15min-20min it
Between.
Then, shown in S2 as shown in figure 1, carry out step 2), polyolefin powder is provided, by the polyolefin powder with it is described
Mixed liquor is mixed, and carries out mixing plasticizing, to form a homogeneous melt.
As an example, in step 2), in the solution that the polyolefin powder and the mixed liquor are mixed to get, the polyene
The mass fraction of hydrocarbon powder between 20wt%-35wt%, the diluent mass fraction between 65wt%-80wt% it
Between, the mass fraction of the nano inorganic powder is between the 0.1%-5% of the mass fraction of the polyolefin powder.
Specifically, the mixed liquor that step 1) is obtained, preferably by the mixed liquor after the ball-milling treatment
It is mixed with polyolefin powder, and carries out the mixing plasticizing, obtained by nano inorganic powder, diluent and polyolefin powder
The homogeneous melt that body is formed, in a preferable example, solution that the polyolefin powder and the mixed liquor are mixed to get
In, the mass fraction of the polyolefin powder between 25wt%-30wt%, the diluent mass fraction between
Between 70wt%-75wt%, the mass fraction of the mass fraction of the nano inorganic powder between the polyolefin powder
Between 1%-3%.Wherein, inorganic particle can be used as heterogeneous nucleation agent in forming process, between PE (polyolefin powder)
The size of ratio can play the role of controlling PE crystallization, and both control ratio has a larger value, such as controls nano inorganic powder
The mass fraction of body is less than the 3% of polyolefin powder quality score, advantageously allows nano inorganic powder and disperses in system
One, the formation for forming the defect on microcosmic is reduced, the homogeneity of integral system is improved；Both control ratio has a smaller value,
The mass fraction for such as controlling nano inorganic powder is greater than the 1% of polyolefin powder quality score, advantageously ensures that the lyophily of diaphragm
Performance.
As an example, carrying out the technique for being kneaded plasticizing includes: to mix the polyolefin powder with described in step 2)
It closes liquid to be added in extruder according to the proportion, the homogeneous melt is formed with abundant mixing plasticizing, wherein in the extruder
Extrusion plasticizing temperature is between 170 DEG C -230 DEG C.
Specifically, form the homogeneous melt in an extruder in a preferable example, i.e., it will be described in step 1)
Mixed liquor and the polyolefin powder are added in extruder according to the proportion, realize mixed milling plasticizing, in addition, here abundant
It is kneaded plasticizing and refers to that most or all of raw material is reacted, to form uniform homogeneous melt.Preferably, extrusion plasticizing
Temperature is preferably between 180 DEG C -220 DEG C, to be conducive to the plasticizing of mixed liquor described in this example Yu polyolefin powder.
As an example, in step 2), the polyolefin powder includes at least one of polyethylene and polypropylene, can also
To be above two combination, the inherent viscosity of the polyolefin powder is between 4.0dl/g-8.0dl/g, the polyolefin
The partial size of powder is between 100 μm -300 μm.Specifically, the inherent viscosity of the polyolefin powder is preferably between 5.0dl/g-
Between 7.0dl/g, the partial size of the polyolefin powder is preferably between 180 μm -220 μm.
Then, shown in S3 as shown in figure 1, step 3) is carried out, cooling treatment is carried out to form a casting to the homogeneous melt
Piece film, and stretch processing is carried out to the slab film.
As an example, carrying out the cooling treatment in step 3) using Quench roller arrangement and forming the slab film, formed
During the slab film, the set temperature of the sharp cooling roll is between 10 DEG C -40 DEG C, the movement velocity of the slab film
Between 2m/min-8m/min.
Specifically, in the step, the homogeneous melt that will be obtained carries out rapid cooling, to form slab film, one compared with
In good example, the temperature (cooling temperature of the i.e. described slab film) of sharp cooling roll setting is preferably between 10 DEG C -40 DEG C
Between 20 DEG C -30 DEG C, movement velocity of the slab film on the Quench roller arrangement be preferably between 4m/min-6m/min it
Between.
As an example, in step 3), carry out the stretch processing technique include in cross directional stretch and longitudinal stretching extremely
Few one kind, wherein when carrying out the cross directional stretch, the stretching ratio stretching in the transverse direction is laterally drawn between 5-13 times
Temperature is stretched between 110 DEG C -125 DEG C；When carrying out the longitudinal stretching, the stretching ratio of the longitudinal stretching is between 3-10
Between times, longitudinal drawing temperature is between 100 DEG C -120 DEG C.
Specifically, formed after the slab film, further include the steps that synchronizing it or asynchronous stretching, it is preferred to use
The mode of asynchronous stretching, wherein the stretching ratio stretching in the transverse direction is preferably between 8-10 times, and transverse drawing temperature is preferred
Between 115 DEG C -120 DEG C, the stretching ratio of the longitudinal stretching is preferably between 4-6 times, and longitudinal drawing temperature is preferred
Between 105 DEG C -110 DEG C.Wherein, draft temperature and stretching ratio carry out certain matching, and matching appropriate can be effective
Increase the degree of orientation of PE strand, obtains the high product of tensile strength.
Finally, carrying out step 4) shown in S4 as shown in figure 1, the diluent in structure obtained by step 3) is removed, and
Winding processing is carried out shaping to the structure after the removal diluent, to obtain the battery composite diaphragm.
As an example, remove the diluent includes extraction process, wherein the extraction of the extraction process in step 4)
Take temperature between 20 DEG C -45 DEG C, wherein in one example, the extraction temperature refers to the temperature of extractant.
As an example, the extractant for carrying out the extraction process includes methylene chloride, hexamethylene, dehydrated alcohol and acetone
One of or a variety of combinations.
As an example, to remove the structure after the diluent carry out the setting temperature of the sizing winding processing between
Between 125 DEG C -135 DEG C.
Specifically, the diluent in the step in removal system, and battery is obtained using the processing of thermal finalization, winding
Composite membrane removes the diluent using extraction process, extraction temperature is preferably between 25 DEG C -40 DEG C in a preferable example
Between, in addition, the temperature of last thermal finalization is preferably between 128 DEG C -132 DEG C.
It should be noted that the present invention mainly passes through the extrusion plasticizing stage for nano inorganic particle and polyolefin, diluent
Blending forms homogeneous system, then obtains final composite diaphragm by slab, stretching, extraction, thermal finalization, winding.Wherein, nanometer nothing
Machine particle is uniformly distributed in the base, plays the role of crystallization nucleating agent in polyolefin forming process, changes the crystallization of polymer
Size and the speed for accelerating crystallization, in addition, nano inorganic material can improve polyolefine material at high temperature with high thermal stability
Shrinkage behavior, the polar functional group on surface can effectively improve the affinity of diaphragm and electrolyte.Polyene provided by the invention
Hydrocarbon/nano inorganic composite diaphragm preparation method is simple, at low cost, is suitable for heavy industrialization continuous production.Obtained electricity
Pond composite diaphragm has excellent high temperature resistance, mechanical strength, excellent electrolyte wettability.
The present invention also provides a kind of battery composite diaphragms, wherein the battery composite diaphragm is preferably provided using the present invention
The preparation method of battery composite diaphragm be prepared, the battery composite diaphragm prepare raw material include nano inorganic powder,
Polyolefin powder and diluent, wherein the battery composite diaphragm be based on the nano inorganic powder, the polyolefin powder with
The diluent is kneaded the homogeneous melt that plasticizing is formed and obtains.
Specifically, the battery composite diaphragm is based on the nano inorganic the present invention also provides a kind of battery composite diaphragm
Powder, the polyolefin powder are kneaded the homogeneous melt that plasticizing is formed with the diluent and obtain, in addition, in the institute of the present embodiment
In the forming process for stating battery composite diaphragm, further include the steps that by the diluent removal in the homogeneous melt, finally
It include the nano inorganic powder and the polyolefin powder, the heterogeneous materials structure that the two is constituted in obtained battery composite diaphragm
At the battery composite diaphragm, it is substantially free of the diluent, certainly, the diluent that residual fraction not yet extracts should not be done
Consider.
As an example, according to parts by weight, the nano inorganic powder, the polyolefin powder and the diluent carry out
In the solution being mixed to get, in the mixing plasticizing process, there can be a three and carry out the shape for being mixed to get a mixed solution
State, in this mixed solution namely the battery composite diaphragm is prepared in raw material, the mass fraction of the polyolefin powder between
Between 20wt%-35wt%, the diluent mass fraction between 65wt%-80wt%, the nano inorganic powder
Mass fraction is between the 0.1%-5% of the mass fraction of the polyolefin powder.
As an example, the nano inorganic powder includes Al2O3、SiO2、TiO2、ZrO2, one of MgO, CaO and SiC
Or a variety of combination；As an example, the partial size of the nano inorganic powder is between 20nm-1000nm；
As an example, the diluent include atoleine, mineral oil, soybean oil, diphenyl ether, in diformazan benzene and toluene
One or more combinations.
As an example, the polyolefin powder includes at least one of polyethylene and polypropylene, the polyolefin powder
Inherent viscosity between 4.0dl/g-8.0dl/g, the partial size of the polyolefin powder is between 100 μm -300 μm.
In a preferable example, the mass fraction of the polyolefin powder is between 25wt%-30wt%, the dilution
Agent mass fraction is between 70wt%-75wt%, and the mass fraction of the nano inorganic powder is between the polyolefin powder
Mass fraction 1%-3% between.The inherent viscosity of the polyolefin powder is preferably between 5.0dl/g-7.0dl/g,
The partial size of the polyolefin powder is preferably between 180 μm -220 μm.
The present invention also provides a kind of lithium ion batteries, including the battery composite diaphragm as described in above-mentioned any one scheme.
In conclusion the present invention provides a kind of battery composite diaphragm, lithium ion battery and preparation method, battery composite diaphragm
Preparation method include: offer nano inorganic powder, and the nano inorganic powder is mixed with diluent, it is mixed to obtain one
Close liquid；Polyolefin powder is provided, the polyolefin powder is mixed with the mixed liquor, and carry out mixing plasticizing, with shape
At a homogeneous melt；Cooling treatment is carried out to form a slab film to the homogeneous melt, and the slab film is stretched
Processing；Step obtains the diluent in structure in removal, and carries out shaping at winding to the structure after the removal diluent
Reason, to obtain the battery composite diaphragm.Through the above scheme, in battery composite diaphragm provided by the invention and preparation method,
Nanometer-level inorganic powder is added in polyalkene diaphragm by the present invention by in-situ blending method, and nano inorganic powder has high fever
Stability can substantially reduce the thermal contraction after lithium battery diaphragm is heated；Nano inorganic powder has biggish specific surface area, table
Face has polar functional group, can improve the lyophily performance between polyalkene diaphragm and electrolyte；Nano inorganic powder is in system
In play heterogeneous nucleating effect, the crystallinity of polyolefin can be increased in polyolefin forming process, improve the mechanical strength of diaphragm.
So the present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (14)
1. a kind of preparation method of battery composite diaphragm, which comprises the steps of:
1) nano inorganic powder is provided, and the nano inorganic powder is mixed with diluent, obtains a mixed liquor；
2) polyolefin powder is provided, the polyolefin powder is mixed with the mixed liquor and carried out mixing plasticizing, to form one
Homogeneous melt；
3) cooling treatment is carried out to form slab film to the homogeneous melt, and stretch processing is carried out to the slab film；And
4) diluent in the obtained structure of step 3) is removed, and the structure after the removal diluent is carried out shaping
Winding processing, to obtain the battery composite diaphragm.
2. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that between step 1) and step 2)
It further comprises the steps of: and ball-milling treatment is carried out to the mixed liquor obtained in step 1)；Carry out time of the ball-milling treatment between
Between 10min-25min.
3. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 1), the nanometer
Inorganic particle includes Al2O3、SiO2、TiO2、ZrO2, one of MgO, CaO and SiC or a variety of combinations；The nanometer nothing
The partial size of machine powder is between 20nm-1000nm.
4. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 1), the dilution
Agent includes one of atoleine, mineral oil, soybean oil, diphenyl ether, dimethylbenzene and toluene or a variety of combinations.
5. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 2), the polyene
In the solution that hydrocarbon powder and the mixed liquor are mixed to get, the mass fraction of the polyolefin powder is between 20wt%-35wt%
Between, the diluent mass fraction is between 65wt%-80wt%, and the mass fraction of the nano inorganic powder is between institute
Between the 0.1%-5% for stating the mass fraction of polyolefin powder.
6. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 2), described in progress
The technique for being kneaded plasticizing includes: to be added to the polyolefin powder and the mixed liquor in extruder according to the proportion, sufficiently mixed
Refining plasticizing forms the homogeneous melt, wherein in the extrusion plasticizing temperature in the extruder between 170 DEG C -230 DEG C.
7. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 2), the polyene
Hydrocarbon powder includes at least one of polyethylene and polypropylene, and the inherent viscosity of the polyolefin powder is between 4.0dl/g-
Between 8.0dl/g, the partial size of the polyolefin powder is between 100 μm -300 μm.
8. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 3), using Quench
Roller arrangement carries out the cooling treatment and forms the slab film, and during forming the slab film, the sharp cooling roll is set
Temperature is determined between 10 DEG C -40 DEG C, and the movement velocity of the slab film is between 2m/min-8m/min.
9. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 3), described in progress
The technique of stretch processing includes at least one of cross directional stretch and longitudinal stretching, wherein the stretching ratio stretching in the transverse direction
Between 5-13 times, transverse drawing temperature is between 110 DEG C -125 DEG C；The stretching ratio of the longitudinal stretching is between 3-10
Between times, longitudinal drawing temperature is between 100 DEG C -120 DEG C.
10. the preparation method of battery composite diaphragm according to claim 1, which is characterized in that in step 4), described in removal
Diluent includes extraction process, wherein the extraction temperature of the extraction process is between 20 DEG C -45 DEG C, the extraction work
The extractant of skill includes one of methylene chloride, hexamethylene, dehydrated alcohol and acetone or a variety of combinations；Described in removal
Structure after diluent carries out the setting temperature of the sizing winding processing between 125 DEG C -135 DEG C.
11. a kind of battery composite diaphragm, which is characterized in that the raw material for preparing of the battery composite diaphragm includes nano inorganic powder
Body, polyolefin powder and diluent, wherein the battery composite diaphragm is based on the nano inorganic powder, the polyolefin powder
Body is kneaded the homogeneous melt that plasticizing is formed with the diluent and obtains.
12. battery composite diaphragm according to claim 11, which is characterized in that according to parts by weight, in the nanometer nothing
In the solution that machine powder, the polyolefin powder and the diluent are mixed to get, the quality point of the polyolefin powder
Number is between 20wt%-35wt%, and the diluent mass fraction is between 65wt%-80wt%, the nano inorganic
The mass fraction of powder is between the 0.1%-5% of the mass fraction of the polyolefin powder.
13. battery composite diaphragm according to claim 11, which is characterized in that the nano inorganic powder includes Al2O3、
SiO2、TiO2、ZrO2, one of MgO, CaO and SiC or a variety of combinations, the partial size of the nano inorganic powder between
Between 20nm-1000nm；The diluent include atoleine, mineral oil, soybean oil, diphenyl ether, in diformazan benzene and toluene
One or more combinations；The polyolefin powder includes at least one of polyethylene and polypropylene, the polyolefin powder
Inherent viscosity between 4.0dl/g-8.0dl/g, the partial size of the polyolefin powder is between 100 μm -300 μm.
14. a kind of lithium ion battery, which is characterized in that compound including the battery as described in any one of claim 11-13
Diaphragm.
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| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
| CN116864916A (en) * | 2023-07-18 | 2023-10-10 | 河北金力新能源科技股份有限公司 | Extremely thin high-strength lithium ion battery diaphragm and preparation method thereof |
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