CN110085793A - A kind of lithium ion battery functional diaphragm and its preparation method and application - Google Patents
A kind of lithium ion battery functional diaphragm and its preparation method and application Download PDFInfo
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- CN110085793A CN110085793A CN201910389251.6A CN201910389251A CN110085793A CN 110085793 A CN110085793 A CN 110085793A CN 201910389251 A CN201910389251 A CN 201910389251A CN 110085793 A CN110085793 A CN 110085793A
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
Abstract
The invention discloses a kind of lithium ion battery functional diaphragms and its preparation method and application, belong to lithium battery diaphragm technical field.A kind of lithium ion battery of the invention functional diaphragm, including barrier film base material and functional material, the functional material are phosphoric acid hydrogen zirconium, and partial size is 25 μm~50 μm；Above-mentioned functional material is directly appended to that porous film material is prepared in barrier film base material, or to be coated in the form of functional coating using barrier film base material as porous membrane surface made of raw material.It can effectively improve the cycle performance of lithium battery diaphragm using technical solution of the present invention, and its preparation process is simple, it is nontoxic, it can also effectively promote the security performance of lithium ion battery.
Description
Technical field
The invention belongs to lithium battery diaphragm technical field, more specifically to a kind of lithium ion battery it is functional every
Film and its preparation method and application.
Background technique
Secondary lithium battery is because having high-energy density, and self discharge is low, memory-less effect, and relatively low internal resistance etc. is prominent
Advantage and be applied to a variety of fixations and portable equipment in.But the cycle performance of lithium ion battery cannot still fully meet people at present
To its increasing need, lithium ion battery is especially used for the electric automobiles having high requirements to course continuation mileage.
Wherein, diaphragm has vital influence, diaphragm to the performance of battery as the important component in lithium ion battery
Capacity, circulation and the security performance etc. that the quality of energy determines the interfacial structure of battery, internal resistance etc., and directly influences battery
Characteristic.
In the prior art, commercialized diaphragm mainly has polyethylene (PE), polypropylene (PP) and ceramics, boehmite coating
Diaphragm, diaphragm can play the role of completely cutting off positive and negative anodes and ionic conduction.But in lithium ion battery use process, positive electrode
In metal cation be easy to happen dissolution in cyclic process, and it is heavy in negative terminal surface from anode by diaphragm to enter cathode
Product, to destroy SEI film, seriously affects the cycle life of battery, and at present for actively promoting the cyclicity of lithium ion battery
Energy aspect is also in conceptual phase.
Such as, the application case that Chinese Patent Application No. is 2014106482760 discloses a kind of permanent dipole with orientation
The lithium iron cell element of the chelating agent of square, an example of the lithium iron cell element be include the more microporous polymer membranes of plane
With the lithium ion battery separator for the chelating agent being bonded to by linker on the more microporous polymer membranes of the plane.Chinese patent Shen
Please number for 2018112824392 an application case disclose a kind of nickel cobalt manganese/nickel cobalt aluminium acid lithium battery and its with functional diaphragm with
The production technology of the diaphragm, the functionality diaphragm include porous membrane substrate and the functional coating coated on substrate surface, described
The coating of the functional coating includes filler, bonding agent, thickener, dispersing agent and stabilizer.Above-mentioned two application case by
Membrane surface is bonded the functional coating of chelating agent or coating containing certain chelating agent, dissolves out chelating agent to lithium ion cell positive
Manganese ion, nickel ion, iron ion captured, so that the cycle performance of battery can be promoted to a certain extent.
For another example, the application case that Chinese Patent Application No. is 2006800453185 discloses a kind of lithium two containing chelating agent
Primary cell electrolyte and the lithium secondary battery for using the electrolyte, this application is by adding certain chelating into electrolyte
Agent improves the cycle performance of battery so as to capture to the ion of dissolution.But the chelating agent in above-mentioned several application cases
Mostly cyclic polymer can be rolled into a ball with nitrogenous or oxygen hat, have certain toxicity, therefore prepared slurry and coating procedure
Bring certain puzzlement.Meanwhile the addition of existing polymeric chelant is also easy to impact the gas permeability of diaphragm, thus shadow
Internal resistance and the self-discharge performance of battery are rung, and detrimental effect is brought to the thermal contraction performance of diaphragm.
Therefore, research is prepared a kind of nontoxic, is easily prepared, be can be improved cycle performance of lithium ion battery, and will not be to electricity
The diaphragm that other service performances in pond impact has great importance.
Summary of the invention
1. to solve the problems, such as
For existing lithium battery diaphragm during recycling, the metal cation in positive electrode is easily dissolved out,
And enter cathode by diaphragm from anode and deposited in negative terminal surface, to influence the problem of performance is recycled in it, the present invention is mentioned
For functional diaphragm of a kind of lithium ion battery and its preparation method and application.It can effectively be mentioned using technical solution of the present invention
The cycle performance of high lithium battery diaphragm, and its preparation process is simple, it is nontoxic, it can also effectively promote the safety of lithium ion battery
Energy.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
First, a kind of lithium ion battery of the invention functional diaphragm, including barrier film base material and functional material, described
Functional material be phosphoric acid hydrogen zirconium, partial size be 25 μm~50 μm.
Further, the functional material is directly appended to that porous film material is prepared in barrier film base material,
Its additive amount is the 2-5% of barrier film base material total amount.
Further, the thickness of the porous membrane: 5~100 μm；Porosity: 20%~80%；Air permeability: 0~
220s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 1~50；Aperture: 10nm~500nm；Preferable porosity be 30~
50%, tortuosity is 3~20, and aperture is 10~50nm.
Further, the functional material is coated in the form of functional coating using barrier film base material as raw material system
At porous membrane surface.
Further, the slurry of the functional coating includes filler, functional material, bonding agent, thickener, divides
Powder and solvent, wherein the dosage of functional additive is the 0.1-20% of functional coating slurry siccative gross weight；The function
Property coating with a thickness of 100nm-20 μm, weight 1g/m2-10g/m2, air permeability is 180~250s/100cc.
Further, the filler is made of one in group aluminium oxide, silica, clay and boehmite
Kind or more than one combination, dosage are the 40-95% of functional coating slurry siccative gross weight；The bonding agent is butylbenzene
Latex, cinnamic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, card wave
One of resin, polyacrylic, urethane acrylate, Polyacrylate Emulsion, polyurethane, carbamate or
More than one combination, dosage are the 0.5-20% of functional coating slurry siccative gross weight；The thickener is selected from carboxylic first
Base sodium cellulosate (CMC), polyethylene oxide, polyethylene glycol oxide, methylcellulose, hydroxypropyl methyl cellulose, hydroxy ethyl fiber
One of element, gelatin, sodium alginate or more than one combination, dosage are the 0.1- of functional coating slurry siccative gross weight
20%；The dispersing agent be selected from polyethylene glycol, polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxyethylene ether,
One of sldium lauryl sulfate, dispersing agent NNO, dispersing agent MF, alkylsulfonate or more than one combination, dosage are function
The 0.1-5% of energy property coating paste siccative gross weight.
Further, the dosage of the functional additive is preferably the 0.5- of functional coating slurry siccative gross weight
8%, the dosage of filler is preferably 80~90%, and the dosage of bonding agent is preferably 2-10%, and the dosage of dispersing agent is preferably
0.1-1%；The thickener is preferably CMC, and the molecular weight of CMC is not less than 5w, dosage 0.1-5%；The functionality
The thickness of coating is preferably 1 μm -5 μm, and weight is preferably 1g/m2-5g/m2。
Second, a kind of preparation method of lithium ion battery of the invention with functional diaphragm, by functional material and diaphragm
Porous film material is prepared by wet processing, dry process, meltblowing method or electrospinning process after substrate mixing,
Described in barrier film base material be one of polyethylene, polypropylene, polyethylene terephthalate and polyimides or a variety of.
Third, a kind of preparation method of lithium ion battery of the invention with functional diaphragm, by each group of functional coating
Divide dispersion mixing together, forms the homogeneous solution that alkaline pH is 5~12, be then coated on using barrier film base material as made of raw material
The one or both sides of porous membrane, up to the functional diaphragm after drying；Wherein functional coating uses micro- intaglio plate coating, leaching
One of painting, transfer coated, intaglio plate coating, spraying, preferably micro- plate gravure coating method.
Fourth, the application of above-mentioned functional diaphragm of the invention in lithium ion battery.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) a kind of lithium ion battery of the invention functional diaphragm, including barrier film base material and functional material, passes through spy
The addition for determining type functional material, the polyolefin general relative to current lithium ion battery (PE/PP) diaphragm and other chelatings
For object adds functional diaphragm, it can be obviously improved the cycle performance of lithium ion battery, and functional material used is nontoxic, no
It can do harm to huamn body.
(2) the functional diaphragm of a kind of lithium ion battery of the invention, by addition phosphoric acid hydrogen zirconium as functional material,
The functionality diaphragm only adsorbs transition metal ions, and will not impact to the migration of lithium ion, while institute is diligent
Energy property material has good antioxygenic property and thermal stability, can reduce aging of diaphragm during cell reaction, together
Shi Buhui impacts the thermal contraction performance of diaphragm or coated separator, and then is conducive to improve the security performance of battery.
(3) the functional diaphragm of a kind of lithium ion battery of the invention, selects phosphoric acid hydrogen zirconium as functional material, the function
Can property auxiliary agent side reaction will not occur with the raw material of other in system and substance, thus will not be to gained diaphragm or coating paste
Other performances impact.
(4) the functional diaphragm of a kind of lithium ion battery of the invention, the functional material is with functional coating
Form is coated on using barrier film base material as porous membrane surface made of raw material, which is easily dispersed in whole slurry coating
In system, it will not occur to reunite and settle.
(5) preparation method of the functional diaphragm of a kind of lithium ion battery of the invention, by functional material directly with every
Film base material mixing produces to obtain functional porous thin-film material through wet process or dry method or other techniques, or by functional material with
The form of functional coating is coated on diaphragm membrane surface, to both can effectively improve the cycle performance of lithium ion battery, together
When will not reduce the gas permeability of diaphragm, so that the internal resistance and self-discharge rate to battery have some superiority.The present invention can also be opposite
The heat resistance for improving diaphragm has steady to promote the safety of battery, and the mature production technology, material cost are lower
Fixed volume production ability.
(6) the functional diaphragm of lithium ion battery of the invention is applied to lithium ion battery, lithium ion can be improved simultaneously
Cycle performance, heat resistance and the security performance of battery, and the diaphragm material is nontoxic, will not cause harm to the human body, using valence
It is worth higher.
Detailed description of the invention
Fig. 1 is embodiment 1, functional diaphragm and suction of 1 septation of comparative example to magnesium-yttrium-transition metal cation in embodiment 3
Attached situation comparison；
Fig. 2 be embodiment 1, in embodiment 3 functional diaphragm and 1 septation of comparative example ionic conductivity comparison diagram；
Fig. 3 is the appearance structure figure of 8 septation basement membrane of embodiment；
Fig. 4 is the appearance structure figure of functional coating in embodiment 8；
Fig. 5 is the capacity retention ratio comparison diagram of embodiment 14,15 and blank sample；
Fig. 6-Fig. 8 be embodiment 14, in embodiment 15 functional diaphragm and 2 septation of comparative example EIS comparison diagram；
Fig. 9 be embodiment 14, in embodiment 15 functional diaphragm and 2 septation of comparative example ventilative range, moisture, battery
Inner walkway and thermal contraction performance correlation data.
Specific embodiment
A kind of lithium ion battery of the invention functional diaphragm, including barrier film base material and functional material, the function
Energy property material is phosphoric acid hydrogen zirconium, and partial size (D90) is 25 μm~50 μm.Currently, also there is researcher's research to pass through in the prior art
Other chelating agents add to improve the cycle performance of lithium ion battery, but chelating agent used is usually cyclic polymer, band
There is nitrogenous or oxygen hat that can roll into a ball, there is certain toxicity；Meanwhile the addition of existing polymeric chelant is also easy to the saturating of diaphragm
Gas and thermal contraction performance impact, to influence the internal resistance of battery, self-discharge performance and security performance.The present invention passes through phosphorus
The addition of sour hydrogen zirconium functional material can effectively improve the cycle performance of lithium ion battery, and the functionality diaphragm is only to transition
Metal ion is adsorbed, and will not be impacted to the migration of lithium ion.Meanwhile it being added relative to other chelates functional
Diaphragm, phosphoric acid hydrogen zirconium functional material used is nontoxic, will not cause harm to the human body, while phosphoric acid hydrogen zirconium functional material adds
Add, especially by the optimal control of its partial size, to guarantee that the gas permeability of diaphragm will not be impacted, and then will not influence
The internal resistance of battery.In addition, phosphoric acid hydrogen zirconium has good heat resistance, 158 DEG C of melting temperature, the thermal contraction of diaphragm coating is tested
MD and the direction TD are respectively less than 1.5% under the conditions of 120 DEG C, to be conducive to improve the security performance of battery.
Specifically, functional material of the invention can be directly appended in barrier film base material through wet processing, dry method work
Porous film material is prepared in skill, meltblowing method or electrospinning process, and additive amount is the 2-5% of barrier film base material total amount.
The barrier film base material can select one of polyethylene, polypropylene, polyethylene terephthalate and polyimides or
It is a variety of, the thickness of gained porous membrane: 5~100 μm；Porosity: 20%~80%；Air permeability: 0~220s/100cc；Intensity:
More than or equal to 35Mpa；Tortuosity: 1~50；Aperture: 10nm~500nm；Preferable porosity be 30~50%, tortuosity be 3~
20, aperture is 10~50nm.
The functional material can also be to be coated in the form of functional coating using barrier film base material as made of raw material
Porous membrane surface.The slurry of functional coating of the present invention includes filler, functional material, bonding agent, thickener, dispersing agent
With solvent (deionized water, the coating paste solid content that additive amount is needed according to producing line to determine), wherein functional additive
Dosage be functional coating slurry siccative gross weight 0.1-20%；The functional coating with a thickness of 100nm-20 μm, weight
Amount is 1g/m2-10g/m2, air permeability is 180~250s/100cc.The preparation process of the coated separator are as follows: starch functional coating
The each component dispersion mixing of material together, forms the homogeneous solution that alkaline pH is 5~12, is then coated on barrier film base material as original
The one or both sides of porous membrane made of expecting, up to the functional diaphragm after drying；Wherein functional coating uses dimple
One of version coating, dip-coating, transfer coated, intaglio plate coating, spraying, preferably micro- plate gravure coating method.
The filler by aluminium oxide, silica, clay and boehmite constitute one of group or it is a kind of with
On combination, dosage be functional coating slurry siccative gross weight 40-95%；The bonding agent is butadiene-styrene latex, phenylpropyl alcohol
Olefin(e) acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, carbomer, poly- third
One of olefin(e) acid class, urethane acrylate, Polyacrylate Emulsion, polyurethane, carbamate or more than one
Combination, dosage be functional coating slurry siccative gross weight 0.5-20%；The thickener is selected from carboxymethyl cellulose
Sodium (CMC), polyethylene oxide, polyethylene glycol oxide, methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, gelatin,
One of sodium alginate or more than one combination, dosage are the 0.1-20% of functional coating slurry siccative gross weight；Institute
The dispersing agent stated is selected from polyethylene glycol, polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxyethylene ether, laruyl alcohol
One of sodium sulphate, dispersing agent NNO, dispersing agent MF, alkylsulfonate or more than one combination, dosage are functional apply
The 0.1-5% of layer slurry siccative gross weight.
In addition, the present invention by selecting phosphoric acid hydrogen zirconium as functional aid, can be improved the cycle performance 5% of battery~
10%, and side reaction will not occurs with the substance of other in system in it, specifically, (1) in basement membrane preparation process, reaction raw materials and
Solvent will not react when such as high density polyethylene (HDPE) and the miscible extrusion of paraffin oil systems with functional aid；(2) coating is starched
Functional aid cannot react with other substances of slurry system in material preparation process；Such as (itself is at alkalinity for dispersing agent
Between pH 8~10) optimal pH (will affect the effect of its active function groups under acid condition between 7~9, cause slurry viscous
Degree decline, stability decline), the weak acid radical ion (it is about 6 that phosphoric acid hydrogen zirconium, which is washed with water to the pH of cleaning solution) in additive is simultaneously
Will not viscosity to slurry entirety and stability impact.Meanwhile phosphoric acid hydrogen zirconium is easily dispersed in whole slurry coating system,
Preferable with the compatibility of other components, static 4h will not still occur to reunite and settle.Coated separator of the invention also has preferably
Antioxygenic property, during battery cycle charge-discharge, oxidation reaction (diaphragm coating towards anode) occurs for anode, it is possible to
Reduce aging of diaphragm during cell reaction.
Further, the dosage of the functional additive is preferably the 0.5- of functional coating slurry siccative gross weight
8%, the dosage of filler is preferably 80~90%, and the dosage of bonding agent is preferably 2-10%, and the dosage of dispersing agent is preferably
0.1-1%；The thickener is preferably CMC, and the molecular weight of CMC is not less than 5w, dosage 0.1-5%；The functionality
The thickness of coating is preferably 1 μm -5 μm, and weight is preferably 1g/m2-5g/m2；The solid content of coating paste is 5-60%, preferably
For 25-45%.
The present invention is further described below combined with specific embodiments below.
Embodiment 1
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyethylene diagrams substrate material and phosphoric acid hydrogen zirconium
Functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 2% of polyethylene diagrams substrate material total amount.The functionality diaphragm passes through
Wet processing is prepared, specifically, by polyethylene raw material, phosphoric acid hydrogen zirconium and paraffin oil melting extrusion, then according to thermotropic phase
Partition method (TIPS) is drawn into porous film, wherein key process parameter are as follows: extruder temperature: 170 DEG C, melt temperature: 160
℃；Casting temperature: 30 DEG C；Draft temperature: 70 DEG C；Stretching speed ratio: 6 times.Porous membrane obtained by the present embodiment has following characteristics:
Thickness: 50 μm；Porosity: 30%；Air permeability: 200s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 15；Aperture:
10nm。
Embodiment 2
A kind of lithium ion battery of the present embodiment functional diaphragm, including polypropylene diaphragm substrate material and phosphoric acid hydrogen zirconium
Functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 3% of polyethylene diagrams substrate material total amount.The functionality diaphragm passes through
Wet processing is prepared, wherein key process parameter are as follows: extruder temperature: 220 DEG C, melt temperature: 205 DEG C；Casting temperature:
10℃；Draft temperature: 90 DEG C；Stretching speed ratio: 4 times.Porous membrane obtained by the present embodiment has following characteristics: thickness: 30 μm；Hole
Gap rate: 50%；Air permeability: 220s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 20；Aperture: 30nm.
Embodiment 3
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyethylene diagrams substrate material and phosphoric acid hydrogen zirconium
Functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 5% of polyethylene diagrams substrate material total amount.The functionality diaphragm passes through
Wet processing is prepared, wherein key process parameter are as follows: extruder temperature: 190 DEG C, melt temperature: 180 DEG C；Casting temperature:
60℃；Draft temperature: 100 DEG C；Stretching speed ratio: 8.5 times.Porous membrane obtained by the present embodiment has following characteristics: thickness: 5 μm；
Porosity: 40%；Air permeability: 20s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 3；Aperture: 50nm.
Comparative example 1
The lithium ion battery separator of this comparative example, preparation process are essentially consisted in embodiment 3, difference: this comparative example
Diaphragm does not add phosphoric acid hydrogen zirconium functional material, i.e. blank sample (KBY) when preparing.
Diaphragm obtained by this comparative example and embodiment 1 and 3 gained diaphragm of embodiment are respectively used to production Soft Roll lithium-ion electric
Pond, wherein positive electrode is ternary material, and negative electrode material is graphite, electroanalysis solvent are as follows: EC, PC, EMC, DMC, DEC, solute are as follows:
LiPF6, additive are as follows: VC.After wherein test condition is 45 DEG C of circulations, 200 circle, dismantles battery and the ion on three kinds of diaphragms is inhaled
Attached situation does EDS analysis, as a result as shown in Figure 1.It can be seen that according to data in Fig. 1 by adding phosphoric acid hydrogen zirconium functionality material
Material as the cycle performance that after functional material, can effectively improve gained diaphragm, the diaphragm to the suction-operated of manganese ion compared with
By force, to meet the use demand for the electric automobiles having high requirements to course continuation mileage.And according to fig. 2 as can be seen that addition
The resistance of gained diaphragm and the resistance of blank sample (1 septation of comparative example) are not much different after phosphoric acid hydrogen zirconium functional material, namely
The addition of phosphoric acid hydrogen zirconium does not influence the migration of lithium ion, and has preferable capture ability to transition metal ions.
Embodiment 4
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyethylene diagrams substrate material and phosphoric acid hydrogen zirconium
Functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 4% of polyethylene diagrams substrate material total amount.The functionality diaphragm passes through
Wet processing is prepared, wherein key process parameter are as follows: extruder temperature: 210 DEG C, melt temperature: 200 DEG C；Casting temperature:
45℃；Draft temperature: 130 DEG C；Stretching speed ratio: 7 times.Porous membrane obtained by the present embodiment has following characteristics: thickness: 100 μm；
Porosity: 20%；Air permeability: 100s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 1；Aperture: 80nm.
Embodiment 5
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyethylene diagrams substrate material and phosphoric acid hydrogen zirconium
Functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 5% of polyethylene diagrams substrate material total amount.The functionality diaphragm passes through
Wet processing is prepared, wherein key process parameter are as follows: extruder temperature: 200 DEG C, melt temperature: 195 DEG C；Casting temperature:
55℃；Draft temperature: 115 DEG C；Stretching speed ratio: 5 times.Porous membrane obtained by the present embodiment has following characteristics: thickness: 80 μm；
Porosity: 80%；Air permeability: 80s/100cc；Intensity: greater than be equal to 35Mpa；Tortuosity: 50；Aperture: 500nm.
Embodiment 6
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyethylene terephthalate barrier film base material
Raw material and phosphoric acid hydrogen zirconium functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 4% of polyethylene diagrams substrate material total amount, should
Functional diaphragm is prepared by dry method simple tension.
Embodiment 7
A kind of lithium ion battery of the present embodiment functional diaphragm, including polyimide diaphragm substrate material and phosphoric acid hydrogen
Zirconium functional material, wherein the additive amount of phosphoric acid hydrogen zirconium is the 2% of polyethylene diagrams substrate material total amount, and the functionality diaphragm is logical
Electrostatic spinning process is crossed to produce to obtain.
Embodiment 8
A kind of functional diaphragm of lithium ion battery of the present embodiment, including diaphragm basement membrane and it is coated on diaphragm membrane surface
Functional coating.The functional coating of the present embodiment include filler, functional material, bonding agent, thickener, dispersing agent and
Solvent, wherein filler is aluminium oxide, and dosage is that (content of each component is to account for coating paste siccative for functional coating gross weight
The percentage of gross weight is calculated, i.e., with it is not aqueous when calculated) 40%；Bonding agent is butadiene-styrene latex, and dosage is function
The 20% of energy property coating gross weight；Thickener selects the combination of sodium carboxymethylcellulose (CMC), methylcellulose and gelatin, uses
Amount is the 20% of functional coating gross weight；Dispersing agent selects polyethylene glycol, and dosage is the 5% of functional coating gross weight；It is described
Functional additive (phosphoric acid hydrogen zirconium) dosage be functional coating gross weight 15%.
The preparation process of the coated separator of the present embodiment are as follows: be blended in one for each component of functional coating is evenly dispersed
It rises, is then coated on using barrier film base material as the one or both sides of porous membrane made of raw material, up to the functionality after drying
Diaphragm；Wherein functional coating is coated using transfer coated mode.Gained functional coating with a thickness of 100nm, weight
For 1g/m2, air permeability 180s/100cc.The scanning figure of the present embodiment septation basement membrane and functional coating such as Fig. 3, Fig. 4 institute
Show.
Embodiment 9
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler is aluminium oxide, clay and boehmite
Combination, dosage are the 95% of functional coating gross weight；Bonding agent is the combination of polyacrylamide and carbamate, dosage
It is the 0.5% of functional coating gross weight；Thickener selects the combination of polyethylene oxide, hydroxyethyl cellulose and sodium alginate,
Dosage is the 0.1% of functional coating gross weight；Dispersing agent selects polyvinylpyrrolidone, sodium n-alkylbenzenesulfonate, laruyl alcohol
The combination of sodium sulphate and dispersing agent MF, dosage are the 4.3% of functional coating gross weight；Functional additive (the phosphoric acid
Hydrogen zirconium) dosage be functional coating gross weight 0.1%.Functional coating is coated using dip coating manner in the present embodiment,
Gained functional coating with a thickness of 10 μm, weight 6g/m2, air permeability 200s/100cc.
Embodiment 10
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler are silica, and dosage is functionality
The 60% of coating gross weight；Bonding agent is Polyacrylate Emulsion, and dosage is the 10% of functional coating gross weight；Thickener
The combination of polyethylene oxide and sodium alginate is selected, dosage is the 9.9% of functional coating gross weight；Dispersing agent selects alkyl poly-
Ethylene oxide ether, dosage are the 0.1% of functional coating gross weight；The dosage of the functional additive (phosphoric acid hydrogen zirconium) is function
The 20% of energy property coating gross weight.Functional coating is coated using spraying method in the present embodiment, gained functional coating
With a thickness of 20 μm, weight 10g/m2, air permeability 250s/100cc.
Embodiment 11
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler is the combination of aluminium oxide and boehmite,
Its dosage is the 80% of functional coating gross weight；Bonding agent is polyurethane, and dosage is the 10% of functional coating gross weight；Thickening
Agent is the combination of sodium carboxymethylcellulose (CMC), polyethylene oxide and sodium alginate, and dosage is functional coating gross weight
1%；Dispersing agent selects the combination of sodium n-alkylbenzenesulfonate, sldium lauryl sulfate and dispersing agent MF, and dosage is functional applies
The 1% of layer gross weight；The dosage of the functional additive (phosphoric acid hydrogen zirconium) is the 8% of functional coating gross weight.The present embodiment
Middle functional coating is coated using micro- plate gravure coating method, gained functional coating with a thickness of 1 μm, weight 1g/m2,
Air permeability is 190s/100cc.
Embodiment 12
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler is the combination of aluminium oxide and clay,
Dosage is the 84.4% of functional coating gross weight；Bonding agent is Polyacrylate Emulsion, and dosage is that functional coating is total
The 10% of weight；Thickener selects hydroxypropyl methyl cellulose, and dosage is the 5% of functional coating gross weight；Dispersing agent selects alkane
Base sulfonate, dosage are the 0.1% of functional coating gross weight；The dosage of the functional additive (phosphoric acid hydrogen zirconium) is function
The 0.5% of energy property coating gross weight.Functional coating is coated using micro- plate gravure coating method in the present embodiment, and gained is functional
Coating with a thickness of 4 μm, weight 3g/m2, air permeability 200s/100cc.
Embodiment 13
A kind of lithium ion battery of the present embodiment is clay and boehmite with functional diaphragm, filler, and dosage is
The 90% of functional coating gross weight；Bonding agent is modified paraffin resin, and dosage is the 2.5% of functional coating gross weight；Thickening
Agent is sodium carboxymethylcellulose (molecular weight is greater than 50,000), and dosage is the 0.1% of functional coating gross weight；Dispersing agent is poly- second
The combination of alkene pyrrolidone and sldium lauryl sulfate, dosage are the 0.4% of functional coating gross weight；The functional addition
The dosage of agent (phosphoric acid hydrogen zirconium) is the 7% of functional coating gross weight.Functional coating uses micro- intaglio plate coating side in the present embodiment
Formula is coated, gained functional coating with a thickness of 5 μm, weight 5g/m2, air permeability 210s/100cc.
Embodiment 14
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler are aluminium oxide, and dosage is functionality
The 87% of coating gross weight；Bonding agent is urethane acrylate, and dosage is the 7% of functional coating gross weight；Thickener is carboxylic
Sodium carboxymethylcellulose pyce (molecular weight is greater than 50,000), dosage are the 3% of functional coating gross weight；Dispersing agent is polyethylene glycol, is used
Amount is the 1% of functional coating gross weight；The dosage of the functional additive (phosphoric acid hydrogen zirconium) is functional coating gross weight
2%.Functional coating is coated using micro- plate gravure coating method in the present embodiment, gained functional coating with a thickness of 3 μm,
Weight is 3g/m2, air permeability 195s/100cc.
Embodiment 15
A kind of functional diaphragm of lithium ion battery of the present embodiment, filler are aluminium oxide, and dosage is functionality
The 84% of coating gross weight；Bonding agent is polyethylene glycol oxide, and dosage is the 5% of functional coating gross weight；Thickener is carboxymethyl
Sodium cellulosate (molecular weight is greater than 50,000), dosage are the 5% of functional coating gross weight；Dispersing agent be polyvinylpyrrolidone with
The combination of dispersing agent MF, dosage are the 1% of functional coating gross weight；The dosage of the functional additive (phosphoric acid hydrogen zirconium)
It is the 5% of functional coating gross weight.Functional coating is coated using micro- plate gravure coating method in the present embodiment, gained function
Property coating with a thickness of 4 μm, weight 3g/m2, air permeability 200s/100cc.
Comparative example 2
A kind of lithium ion battery separator (blank sample) of this comparative example, including diaphragm basement membrane and be coated on diaphragm membrane surface
Ceramic coating, the component of the ceramic coating is identical as embodiment 15, difference essentially consist in: phosphoric acid hydrogen zirconium functionality does not add
Add agent.
By the blank sample diaphragm in embodiment 14 and the functional diaphragm of 15 gained of embodiment and comparative example 2 (without functionality
Coating) respectively production form soft-package battery, positive electrode is ternary material, and negative electrode material is graphite, electroanalysis solvent are as follows: EC, PC,
EMC, DMC, DEC, solute are as follows: LiPF6, additive are as follows: VC.Capacity retention ratio test is carried out to different samples, as a result such as Fig. 5 institute
Show, as can be seen from Figure, after 300cycles is recycled, made of embodiment 14 and the functional diaphragm of 15 gained of embodiment
Battery is also able to maintain higher capacity retention ratio, and about 93.43% and 90.79%, and the capacity retention ratio of blank sample (KBY) exists
86.97% is decayed to after 300 circle of circulation.
Fig. 6-Fig. 8 is respectively blank sample (KBY), 5 circle of ZP-2% and ZP-5% sample circulation, and 10 circles, 15 circles, 20 enclose, and 25
Circle, 30 circles, 35 circles, the electrochemical impedance map of 40 circles, as can be seen from Figure, the 5th encloses initial value, and the internal resistance of blank sample is with regard to remote
Greater than the value of comparative sample ZP-2% and ZP-5%.After the circle of circulation 40, the internal resistance of ZP-2% and ZP-5% are compared to blank sample
(KBY) still have great advantage.As seen from Figure 9, the ventilative range of ZP-2% and ZP-5% sample, moisture, the internal resistance of cell
Test is closer to ceramic coating (blank sample), but its thermal contraction performance is significantly better than ceramic coating, therefore improves battery
Security performance.
Claims (10)
1. a kind of functional diaphragm of lithium ion battery, it is characterised in that: including barrier film base material and functional material, the function
Energy property material is phosphoric acid hydrogen zirconium, and partial size is 25 μm~50 μm.
2. a kind of functional diaphragm of lithium ion battery according to claim 1, it is characterised in that: the functional material
Material is directly appended to that porous film material is prepared in barrier film base material, and additive amount is the 2-5% of barrier film base material total amount.
3. a kind of functional diaphragm of lithium ion battery according to claim 2, it is characterised in that: the porous membrane
Thickness: 5~100 μm；Porosity: 20%~80%；Air permeability: 0~220s/100cc；Intensity: greater than be equal to 35Mpa；It is tortuous
Degree: 1~50；Aperture: 10nm~500nm；Preferable porosity is 30~50%, and tortuosity is 3~20, and aperture is 10~50nm.
4. a kind of functional diaphragm of lithium ion battery according to claim 1, it is characterised in that: the functional material
Material in the form of functional coating to be coated on using barrier film base material as porous membrane surface made of raw material.
5. a kind of functional diaphragm of lithium ion battery according to claim 4, it is characterised in that: the functional coating
Slurry include filler, functional material, bonding agent, thickener, dispersing agent and solvent, the wherein dosage of functional additive
For the 0.1-20% of functional coating slurry siccative gross weight；The functional coating with a thickness of 100nm-20 μm, weight 1g/
m2-10g/m2, air permeability is 180~250s/100cc.
6. a kind of functional diaphragm of lithium ion battery according to claim 5, it is characterised in that: the filler is
One of aluminium oxide, silica, clay and the constituted group of boehmite or more than one combination, dosage are functionality
The 40-95% of coating paste siccative gross weight；The bonding agent is butadiene-styrene latex, cinnamic acid, polyacrylamide, polyethylene
Alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, modified paraffin resin, carbomer, polyacrylic, urethane acrylate,
One of Polyacrylate Emulsion, polyurethane, carbamate or more than one combination, dosage are functional apply
The 0.5-20% of layer slurry siccative gross weight；The thickener is selected from sodium carboxymethylcellulose (CMC), polyethylene oxide, polyoxy
Change ethylene, methylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, gelatin, one of sodium alginate or it is a kind of with
On combination, dosage be functional coating slurry siccative gross weight 0.1-20%；The dispersing agent is selected from polyethylene glycol, gathers
Vinylpyrrolidone, sodium n-alkylbenzenesulfonate, alkyl polyoxyethylene ether, sldium lauryl sulfate, dispersing agent NNO, dispersing agent MF,
One of alkylsulfonate or more than one combination, dosage are the 0.1-5% of functional coating slurry siccative gross weight.
7. a kind of functional diaphragm of lithium ion battery according to claim 6, it is characterised in that: the functional addition
The dosage of agent is preferably the 0.5-8% of functional coating slurry siccative gross weight, and the dosage of filler is preferably 80~90%, bonding
The dosage of agent is preferably 2-10%, and the dosage of dispersing agent is preferably 0.1-1%；The thickener is preferably CMC, point of CMC
Son amount is not less than 5w, dosage 0.1-5%；The thickness of the functional coating is preferably 1 μm -5 μm, and weight is preferably
1g/m2-5g/m2。
8. a kind of lithium ion battery as claimed in claim 2 or claim 3 preparation method of functional diaphragm, it is characterised in that: will
Functional material is prepared into after mixing with barrier film base material by wet processing, dry process, meltblowing method or electrospinning process
To porous film material, wherein the barrier film base material is that polyethylene, polypropylene, polyethylene terephthalate and polyamides are sub-
One of amine is a variety of.
9. a kind of lithium ion battery as described in any one of claim 4-7 preparation method of functional diaphragm, feature
It is: together by each component dispersion mixing of functional coating slurry, forms the homogeneous solution that alkaline pH is 5~12, then
It is coated on using barrier film base material as the one or both sides of porous membrane made of raw material, up to the functional diaphragm after drying；Its
Middle functional coating uses one of micro- intaglio plate coating, dip-coating, transfer coated, intaglio plate coating, spraying, preferably micro- intaglio plate coating
Mode.
10. a kind of application such as functional diaphragm of any of claims 1-7 in lithium ion battery.
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| CN110808349A (en) * | 2019-09-29 | 2020-02-18 | 南通百川新材料有限公司 | Preparation method of lithium ion battery diaphragm applied in wide temperature range |
| CN111081953A (en) * | 2019-11-20 | 2020-04-28 | 河北金力新能源科技股份有限公司 | Diaphragm slurry for efficiently capturing metal ions, diaphragm and application of diaphragm |
| CN112670672A (en) * | 2020-12-28 | 2021-04-16 | 横店集团东磁股份有限公司 | Diaphragm for high-temperature storage, preparation method thereof and lithium ion battery |
| CN112768841A (en) * | 2021-01-15 | 2021-05-07 | 惠州锂威电子科技有限公司 | Diaphragm for lithium ion battery and lithium ion battery |
| CN113078412A (en) * | 2019-12-17 | 2021-07-06 | 山东海科创新研究院有限公司 | Flame-retardant composite diaphragm, preparation method thereof and lithium ion battery |
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