CN103956449B - Lithium ion secondary battery as well as isolating membrane and preparation method of lithium ion secondary battery - Google Patents
Lithium ion secondary battery as well as isolating membrane and preparation method of lithium ion secondary battery Download PDFInfo
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- CN103956449B CN103956449B CN201410194248.6A CN201410194248A CN103956449B CN 103956449 B CN103956449 B CN 103956449B CN 201410194248 A CN201410194248 A CN 201410194248A CN 103956449 B CN103956449 B CN 103956449B
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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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- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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
The invention provides a lithium ion secondary battery as well as an isolating membrane and a preparation method of lithium ion secondary battery. The isolating membrane of the lithium ion secondary battery comprises a multi-hole base material, wherein at least one surface of the multi-hole base material is coated with a fibrous layer; the fibrous layer comprises an organic fibre for conducting an lithium ion and inorganic matter connected with the organic fibre, and the surface of the inorganic matter contains hydroxyl; the lithium ion secondary battery comprises a positive pole piece, a negative pole piece, an isolating membrane as well as an electrolyte, wherein the isolating membrane is arranged between the positive pole piece and the negative pole piece at an interval and is the isolating membrane of the lithium ion secondary battery. The isolating membrane provided by the invention has high electrochemical stability and ionic conductivity. The lithium ion secondary battery provided by the invention has high first coulombic efficiency and the good cycling property and the rate property, and the self discharge property of the lithium ion secondary battery is low.
Description
Technical field
The present invention relates to cell art, more particularly, to a kind of lithium rechargeable battery and its barrier film and preparation side
Method.
Background technology
The security performance of lithium rechargeable battery receives much concern always, in order to improve the security of lithium rechargeable battery
Can, prevent on fire or blast etc., people coat one layer of ceramic layer on the barrier film of lithium rechargeable battery.This ceramic layer
On the one hand positive electrode and barrier film can be isolated, prevent barrier film from being aoxidized by positive pole, on the other hand can pierce through in generation barrier film,
The effect supporting barrier film can be played when short-circuit, prevent barrier film from shrinking, subsiding, in order to avoid causing more serious situation.But isolation
The ceramic layer on film surface there is also following problem：1. pottery itself is unable to conducting lithium ions, if ceramic layer is blocked up or overstocked,
The lithium ion percent of pass that barrier film can be led to substantially reduces, and then the ionic conductivity of barrier film is reduced；2. barrier film
Ceramic layer easily comes off, thus ineffective；3. the ceramic layer of barrier film does not have caking property to positive plate and negative plate, lead to every
Interface between film and positive plate and negative plate is highly susceptible to destroy.
Content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium rechargeable battery and its every
From film and preparation method, described barrier film has higher electrochemical stability and ionic conductivity, described lithium ion secondary electricity
Pond has higher coulombic efficiency first and preferable cycle performance and high rate performance, and the self discharge of lithium rechargeable battery
Less.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of lithium rechargeable battery
Barrier film, it includes porous substrate.It is coated with fibrage at least one surface of described porous substrate；Described fibrage comprises
Can the organic fiber of conducting lithium ions and the inorganic matter of the surface hydroxyl that described organic fiber is connected.
In a second aspect of the present invention, the invention provides a kind of preparation method of the barrier film of lithium rechargeable battery,
For preparing the barrier film of the lithium rechargeable battery of first aspect present invention, it includes step：(1) dissolve the binder in molten
In agent 1-METHYLPYRROLIDONE (NMP), heat up and stir, obtain binder solution；(2) add in the binder solution of gained
Organic fiber, heats up and stirs, and carries out ultrasonic disperse afterwards, obtains organic fiber solution；(3) to the organic fiber solution of gained
The inorganic matter of middle addition surface hydroxyl, is sufficiently stirred for making it be uniformly dispersed, and carries out ultrasonic disperse afterwards, forms organic fiber pulp
Material；(4) the organic fiber slurry of gained is uniformly coated at least one surface of porous substrate, is toasted with baking oven afterwards
It is dried and removes solvent, obtain the barrier film of lithium rechargeable battery, wherein, described organic fiber slurry is formed after baking is dried
Fibrage.
In a third aspect of the present invention, the invention provides a kind of lithium rechargeable battery, it includes：Positive plate；Negative pole
Piece；Barrier film, is interval between positive plate and negative plate；And electrolyte.Described barrier film is the lithium of first aspect present invention
The barrier film of ion secondary battery.
Beneficial effects of the present invention are as follows：
1. the organic fiber in fibrage described in can with conducting lithium ions so that the percent of pass of lithium ion is higher, and then every
Higher from the ionic conductivity of film.
2., after organic fiber described in is through the inorganic matter link enhancement of surface hydroxyl, it leads the performance of lithium ion significantly
Lifting, and described organic fiber can play, on the surface of barrier film, the effect intercepting and supporting, and then ensure that lithium ion two
The security performance of primary cell, will not reduce the ionic conductivity of barrier film simultaneously.
Specific embodiment
The following detailed description of the lithium rechargeable battery according to the present invention and its barrier film and preparation method and embodiment,
Comparative example and test result.
The barrier film of lithium rechargeable battery according to a first aspect of the present invention is described first.
The barrier film of lithium rechargeable battery according to a first aspect of the present invention includes porous substrate.Described porous substrate
It is coated with fibrage at least one surface；Described fibrage comprise can conducting lithium ions organic fiber and will be described organic
The inorganic matter of the surface hydroxyl that fiber connects.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, described porous substrate is selected from
One of PE film, PP film and PE/PP composite membrane.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, described fibrolaminar thickness can
For 1 μm～5 μm.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, described fibrolaminar porosity
Can be 10%～80%.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, described organic fiber is selected from
The homopolymers that formed by monomer 1, the copolymer being obtained by the aliphatic olefin copolymerization of monomer 1 and C2～C6 and by monomer 1 with
One of copolymer that aromatic olefin copolymerization obtains；
Wherein, M is selected from one of H, alkali metal and alkaline-earth metal；R1、R2Aliphatic independently selected from H, C1～C6
One of group and aromatic radical.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the quality of described organic fiber
Can be the 65%～99% of described fibrolaminar gross mass.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the nothing of described surface hydroxyl
The quality of machine thing can be the 1%～35% of described fibrolaminar gross mass.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the diameter of described organic fiber
Can be 50nm～200nm.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the major diameter of described organic fiber
Ratio can be 5～1000.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the nothing of described surface hydroxyl
The hydroxy radical content on the surface of machine thing can be 100/μm2～1000/μm2.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the nothing of described surface hydroxyl
Machine thing is selected from one or more of aerosil, gaseous oxidation aluminium and gaseous oxidation titanium.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the nothing of described surface hydroxyl
The specific surface area of machine thing can be 50m2/ g～500m2/g.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the nothing of described surface hydroxyl
The particle diameter of the particle of machine thing can be 1nm～1000nm.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, described fibrage can comprise to glue
Knot agent.
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the optional autohemagglutination of described binding agent
One of vinylpyrrolidone (PVP), polyvinyl alcohol (PVA), Kynoar (PVDF).
In the barrier film of lithium rechargeable battery described according to a first aspect of the present invention, the quality of described binding agent can
For described fibrolaminar gross mass 0%～10%.
Secondly the preparation method of the explanation barrier film of lithium rechargeable battery according to a second aspect of the present invention.
The preparation method of the barrier film of lithium rechargeable battery according to a second aspect of the present invention, for preparing the present invention
The barrier film of the lithium rechargeable battery of one side, including step：(1) dissolve the binder in solvent N-methyl pyrilidone
(NMP), in, heat up and stir, obtain binder solution；(2) add organic fiber in the binder solution of gained, heat up simultaneously
Stirring, carries out ultrasonic disperse afterwards, obtains organic fiber solution；(3) surface is added to contain hydroxyl in the organic fiber solution of gained
The inorganic matter of base, is sufficiently stirred for making it be uniformly dispersed, and carries out ultrasonic disperse afterwards, forms organic fibre stuff；(4) by gained
Organic fiber slurry is uniformly coated at least one surface of porous substrate, is dried with baking oven baking afterwards and removes solvent,
Obtain the barrier film of lithium rechargeable battery, wherein, described organic fiber slurry forms fibrage after baking is dried.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(1), in, the temperature of intensification can be 20 DEG C～35 DEG C.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(1), in, the rotating speed of stirring can be 500RPM～2000RPM.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(1), in, the time of stirring can be 0.5h～4h.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(1), in, the concentration of binder solution can be 0.1g/L～500g/L.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(2), in, the temperature of intensification can be 20 DEG C～35 DEG C.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(2), in, the rotating speed of stirring can be 500RPM～2000RPM.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(2), in, the time of stirring can be 0.5h～4h.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(2), in, the time of ultrasonic disperse can be 10min～30min.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(2), in, in organic fiber solution, the solid content of organic fiber can be 10%～90%.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(3), in, the rotating speed of stirring can be 500RPM～2000RPM.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(3), in, the time of stirring can be 2h～6h.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(3), in, the time of ultrasonic disperse can be 10min～30min.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(3), in, in organic fiber slurry, the weight/mass percentage composition of inorganic modifier can be 0.5%～70%.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(4), in, the dry temperature of baking oven baking can be 60 DEG C～85 DEG C.
In the preparation method of the barrier film of lithium rechargeable battery described according to a second aspect of the present invention, in step
(4), in, the baking oven baking dry time can be 2min～5min.
Lithium rechargeable battery according to a third aspect of the present invention is described again.
Lithium rechargeable battery according to a third aspect of the present invention, including：Positive plate；Negative plate；Barrier film, is just interval in
Between pole piece and negative plate；And electrolyte.Described barrier film is the lithium rechargeable battery according to first aspect present invention
Barrier film.
The embodiment of the following lithium rechargeable battery illustrating according to the present invention and its barrier film and preparation method, contrast
Example.
Embodiment 1
The preparation of the barrier film of A lithium rechargeable battery
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 92g fibre diameter is polyacrylic acid (PAA) fiber that 100nm, draw ratio are 140 (by monomer 1-
1 formation), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir under the rotating speed of 2000RPM
2h, is uniformly dispersed to organic fiber, after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution,
Obtain organic fiber solution, afterwards this organic fiber solution is sealed standby；
(3) hydroxy radical content accurately weighing 3g surface is 200/μm2, specific surface area be 300m2/ g, grain diameter are
The aerosil of 150nm, and be added in the organic fiber solution of step (2) gained, afterwards under the rotating speed of 1000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2.5 μm, and fibrolaminar porosity is 30%.
The preparation of the positive plate of B lithium rechargeable battery
By positive electrode active materials LiCoO2, conductive agent Super-P, binding agent PVDF in mass ratio 97:1.6:1.4 be dissolved in molten
In agent 1-METHYLPYRROLIDONE, stir and make anode sizing agent, then anode sizing agent is uniformly coated on plus plate current-collecting body aluminium
On paper tinsel, dry, obtain positive pole diaphragm, afterwards through colding pressing, cut into slices, soldering polar ear, obtain the positive plate of lithium rechargeable battery.
The preparation of the negative plate of C lithium rechargeable battery
By negative active core-shell material graphite, conductive agent Super-P, thickener CMC, bonding agent SBR in mass ratio 96:1.0:
1.0:1.5 are dissolved in solvent deionized water, stir and make cathode size, then cathode size are uniformly coated on negative pole collection
On fluid Copper Foil, dry, obtain cathode membrane, afterwards through colding pressing, cut into slices, soldering polar ear, obtain lithium rechargeable battery
Negative plate.
The preparation of the electrolyte of D lithium rechargeable battery
Using LiPF6With solvent (ethylene carbonate:Diethyl carbonate:Methyl ethyl carbonate:Ethenylidene carbonic ester=
8:85:5:2, mass ratio) with 8:The solution that 92 mass ratio is formulated is as the electrolyte of lithium rechargeable battery.
The preparation of E lithium rechargeable battery
The positive plate of preparation, negative plate and barrier film winding is assembled into naked battery core, drying, the electrolysis of injection preparation
After the operations such as liquid, encapsulation, obtain lithium rechargeable battery.
Embodiment 2
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinyl alcohol (PVA) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP), heats up
To 45 DEG C, and stir 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed standby；
(2) accurately weighing 85g fibre diameter is polyacrylic acid (PAA) fiber that 90nm, draw ratio are 222 (by monomer 1-1
Formed), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM,
It is uniformly dispersed to organic fiber, after the completion of stirring, then carry out ultrasonic disperse 15min, to remove small bubble in solution, obtain
This organic fiber solution is sealed standby by organic fiber solution afterwards；
(3) hydroxy radical content accurately weighing 10g surface is 500/μm2, specific surface area be 200m2/ g, grain diameter are
The aerosil of 250nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2 μm, and fibrolaminar porosity is 38%.
Embodiment 3
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent Kynoar (PVDF) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP), rises
Temperature is to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtains binder solution, seals this binder solution standby afterwards；
(2) accurately weighing 81g fibre diameter is polyacrylic acid (PAA) fiber that 100nm, draw ratio are 120 (by monomer 1-
1 formation), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir under the rotating speed of 2000RPM
2h, is uniformly dispersed to organic fiber, after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution,
Obtain organic fiber solution, afterwards this organic fiber solution is sealed standby；
(3) hydroxy radical content accurately weighing 14g surface is 100/μm2, specific surface area be 50m2/ g, grain diameter are
The aerosil of 1000nm, and being added in the organic fiber solution of step (2) gained, the rotating speed of 2000RPM more afterwards
Lower stirring 2h, makes aerosil be uniformly dispersed, and carries out ultrasonic disperse 15min more afterwards, to remove small gas in solution
Bubble, forms organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2 μm, and fibrolaminar porosity is 19%.
Embodiment 4
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) it is added without binding agent；
(2) accurately weigh 65g fibre diameter be 100nm, draw ratio be 50, the organic fiber that formed by monomer 1-2, and
It is added in the binder solution of step (1) gained, is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, to organic fibre
Dimension is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, obtains organic fiber
This organic fiber solution is sealed standby by solution afterwards；
(3) hydroxy radical content accurately weighing 35g surface is 270/μm2, specific surface area be 500m2/ g, grain diameter are
The aerosil of 1nm, and be added in the organic fiber solution of step (2) gained, stir under the rotating speed of 2000RPM more afterwards
Mix 2h, so that aerosil is uniformly dispersed, carry out ultrasonic disperse 15min more afterwards, to remove small bubble in solution, shape
Become organic fiber slurry, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2.5 μm, and fibrolaminar porosity is 80%.
Embodiment 5
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 70g fibre diameter is Lithium polyacrylate fiber that 60nm, draw ratio are 667 (by monomer 1-3 shape
Become), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, extremely
Organic fiber is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, is had
This organic fiber solution is sealed standby by machine fiber solution afterwards；
(3) hydroxy radical content accurately weighing 25g surface is 400/μm2, specific surface area be 300m2/ g, grain diameter are
The aerosil of 80nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2 μm, and fibrolaminar porosity is 26%.
Embodiment 6
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 80g fibre diameter is polymethylacrylic acid fiber that 80nm, draw ratio are 38 (by monomer 1-4 shape
Become), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, extremely
Organic fiber is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, is had
This organic fiber solution is sealed standby by machine fiber solution afterwards；
(3) hydroxy radical content accurately weighing 15g surface is 350/μm2, specific surface area be 100m2/ g, grain diameter are
The aerosil of 130nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 1 μm, and fibrolaminar porosity is 65%.
Embodiment 7
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 75g fibre diameter is polymethylacrylic acid lithium fiber that 50nm, draw ratio are 1000 (by monomer
1-5 is formed), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir under the rotating speed of 2000RPM
2h, is uniformly dispersed to organic fiber, after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution,
Obtain organic fiber solution, afterwards this organic fiber solution is sealed standby；
(3) hydroxy radical content accurately weighing 20g surface is 400/μm2, specific surface area be 200m2/ g, grain diameter are
The aerosil of 250nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 1.5 μm, and fibrolaminar porosity is 60%.
Embodiment 8
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 90g fibre diameter is calcium polyacrylate (CPA) fiber that 70nm, draw ratio are 14 (by monomer 1-6 shape
Become), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, extremely
Organic fiber is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, is had
This organic fiber solution is sealed standby by machine fiber solution afterwards；
(3) hydroxy radical content accurately weighing 5g surface is 100/μm2, specific surface area be 300m2/ g, grain diameter are
The aerosil of 600nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2.5 μm, and fibrolaminar porosity is 50%.
Embodiment 9
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 10g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weigh 84g fibre diameter be 50nm, draw ratio be 400, obtained by monomer 1-1 and ethylene copolymer
Organic fiber, and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir under the rotating speed of 2000RPM
2h, is uniformly dispersed to organic fiber, after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution,
Obtain organic fiber solution, afterwards this organic fiber solution is sealed standby；
(3) hydroxy radical content accurately weighing 6g surface is 180/μm2, specific surface area be 50m2/ g, grain diameter are
The aerosil of 1000nm, and being added in the organic fiber solution of step (2) gained, the rotating speed of 2000RPM more afterwards
Lower stirring 2h, makes aerosil be uniformly dispersed, and carries out ultrasonic disperse 15min more afterwards, to remove small gas in solution
Bubble, forms organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 1.5 μm, and fibrolaminar porosity is 40%.
Embodiment 10
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) it is added without binding agent；
(2) accurately weigh 99g fibre diameter be 70nm, draw ratio be 129, by monomer 1-1 and 1,3- pentadiene copolymerization
The organic fiber obtaining, and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and the rotating speed in 2000RPM
Lower stirring 2h, is uniformly dispersed to organic fiber, after the completion of stirring, then carries out ultrasonic disperse 15min, small in solution to remove
Bubble, obtains organic fiber solution, seals this organic fiber solution standby afterwards；
(3) hydroxy radical content accurately weighing 1g surface is 350/μm2, specific surface area be 300m2/ g, grain diameter are
The aerosil of 160nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage, the fibre of one side after the drying
The thickness of dimension layer is 2 μm, and fibrolaminar porosity is 28%.
Embodiment 11
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weigh 77g fibre diameter be 200nm, draw ratio be 5, the organic fiber that formed by monomer 1-7, and
It is added in the binder solution of step (1) gained, is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, to organic fibre
Dimension is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, obtains organic fiber
This organic fiber solution is sealed standby by solution afterwards；
(3) hydroxy radical content accurately weighing 18g surface is 700/μm2, specific surface area be 300m2/ g, grain diameter are
The aerosil of 360nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 0.5 μm, and fibrolaminar porosity is 60%.
Embodiment 12
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weigh 73g fibre diameter be 100nm, draw ratio be 40, the organic fiber that obtained by monomer 1-8, and
It is added in the binder solution of step (1) gained, is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, to organic fibre
Dimension is uniformly dispersed, and after the completion of stirring, then carries out ultrasonic disperse 15min, to remove small bubble in solution, obtains organic fiber
This organic fiber solution is sealed standby by solution afterwards；
(3) hydroxy radical content accurately weighing 22g surface is 800/μm2, specific surface area be 200m2/ g, grain diameter are
The gaseous oxidation aluminium of 250nm, and be added in the organic fiber solution of step (2) gained, stir under the rotating speed of 2000RPM more afterwards
Mix 2h, so that aerosil is uniformly dispersed, carry out ultrasonic disperse 15min more afterwards, to remove small bubble in solution, shape
Become organic fiber slurry, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 0.5 μm, and fibrolaminar porosity is 70%.
Embodiment 13
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weighing 69g fibre diameter is polyacrylic acid (PAA) fiber that 90nm, draw ratio are 56 (by monomer 1-1
Formed), and be added in the binder solution of step (1) gained, it is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM,
It is uniformly dispersed to organic fiber, after the completion of stirring, then carry out ultrasonic disperse 15min, to remove small bubble in solution, obtain
This organic fiber solution is sealed standby by organic fiber solution afterwards；
(3) hydroxy radical content accurately weighing 26g surface is 900/μm2, specific surface area be 300m2/ g, grain diameter are
The gas phase titanium dioxide of 160nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 1.5 μm, and fibrolaminar porosity is 27%.
Embodiment 14
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weigh 66g fibre diameter be 100nm, draw ratio be 150, obtained with styrene copolymerized by monomer 1-1
Organic fiber, and be added in the binder solution of step (1) gained, be warming up to 45 DEG C, and stir under the rotating speed of 2000RPM
Mix 2h, be uniformly dispersed to organic fiber, after the completion of stirring, then carry out ultrasonic disperse 15min, to remove small gas in solution
Bubble, obtains organic fiber solution, seals this organic fiber solution standby afterwards；
(3) hydroxy radical content accurately weighing 29g surface is 800/μm2, specific surface area be 400m2/ g, grain diameter are
The aerosil of 600nm, and be added in the organic fiber solution of step (2) gained, afterwards again under the rotating speed of 2000RPM
Stirring 2h, makes aerosil be uniformly dispersed, carries out ultrasonic disperse 15min more afterwards, to remove small bubble in solution,
Form organic fibre stuff, afterwards will be standby for the sealing shading of this organic fiber slurry；
(4) the organic fiber slurry of step (3) gained is uniformly coated on two surfaces of porous substrate PP film, it
Toast 2h in the baking oven at 45 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, two-sided fibre
In dimension layer, every layer of thickness is 2.5 μm, and fibrolaminar porosity is 10%.
Comparative example 1
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A), polyacrylic acid (PAA) fiber is processed without aerosil, every layer of thickness in two-sided fibrage
Spend for 2.5 μm, fibrolaminar porosity is 8%.
Comparative example 2
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A), is not coated processing.
Comparative example 3
Prepare lithium rechargeable battery according to the method for embodiment 1, simply in the system of the barrier film of lithium rechargeable battery
Standby (i.e. in step A)：
(1) 5g binding agent polyvinylpyrrolidone (PVP) is dissolved in 1000ml solvent N-methyl pyrilidone (NMP)
In, it is warming up to 45 DEG C, and stirs 2h under the rotating speed of 2000RPM, obtain binder solution, afterwards this binder solution is sealed
Standby；
(2) accurately weigh the Fanglun 1414 that 95g fibre diameter is that 100nm, draw ratio are 30, and
It is added in the solution of step (1) gained, is warming up to 45 DEG C, and stir 2h under the rotating speed of 2000RPM, to organic fiber dispersion
Uniformly, after the completion of stirring, then carry out ultrasonic disperse 15min, to remove small bubble in solution, obtain organic fiber slurry,
Afterwards this organic fiber slurry is sealed standby；
(3) the organic fiber coating paste of step (2) gained is uniformly coated on two surfaces of porous substrate PP film
On, toast 4h in the baking oven at 85 DEG C afterwards, remove solvent, described organic fiber slurry forms fibrage after the drying, double
In the fibrage in face, every layer of thickness is 2.5 μm, and fibrolaminar porosity is 15%.
The finally lithium rechargeable battery of the explanation present invention and its test process of barrier film and preparation method and test
Result.
1. the air permeability test of barrier film
Barrier film is placed on Gurly value tester, under 20mm mercury column, measures the gas that volume is 100cc and flow through
0.1cm2The time needed for barrier film.
2. the electrochemical stability test of barrier film
By barrier film, two panels stainless steel substrates form button cell, inject electrolyte, access electrochemical workstation, 0V～
In the voltage range of 5V, apply the disturbance of 0.05mV/s, from CV in figure, seen whether redox peaks, to have determined barrier film
Electrochemical stability.
3. the electrical conductivity test of barrier film
Barrier film, two panels stainless steel substrates are formed button cell, injects electrolyte, access electrochemical workstation, test should
The AC impedance of button cell, frequency range is 1Hz～50000Hz, frequency sweep 5Hz, and analog circuit is R (CR), is simulated by it
AC impedance can calculate barrier film electrical conductivity size.
4. the cycle performance test of lithium rechargeable battery
At 25 DEG C, with 0.7C multiplying power constant-current charge to voltage as 4.35V, with 4.35V constant-voltage charge to electric current it is afterwards
0.05C, then with 1C multiplying power constant-current discharge to voltage as 3.0V, this is a charge and discharge cycles process, repeatedly this fills for 500 times
Discharge cycles.
The electric discharge after the discharge capacity after the circulation of capability retention=500th time/first time circulation after 500 circulations is held
Amount × 100%.
5. the high rate performance test of lithium rechargeable battery
At 25 DEG C, with 0.7C multiplying power constant-current charge to voltage as 4.35V, with 4.35V constant-voltage charge to electric current it is afterwards
0.05C, the discharge capacity then respectively with the multiplying power constant-current discharge of 0.5C and 2C to voltage as 3.0V, under record different multiplying.
Discharge capacity × 100% of the discharge capacity/0.5C of the discharge-rate=2C of lithium rechargeable battery.
6. the K value test of lithium rechargeable battery
At 25 DEG C, with 0.7C multiplying power constant-current charge to voltage as 3.85V, normal temperature stands 48h, test lithium ion secondary electricity
The voltage in pond, is designated as V1, then lithium rechargeable battery is placed in placement 48h at 45 DEG C, test lithium rechargeable battery again
Voltage, is designated as V2, the K value=V of lithium rechargeable battery1/V2-1.
Table 1 provides parameter and the performance test results of embodiment 1-14 and comparative example 1-3.
Next the performance test results of embodiment 1-14 and comparative example 1-3 are analyzed.
As can be seen that the present invention's is coated with fibrage and organic fibre from the contrast of embodiment 1-14 and comparative example 1-2
The barrier film that dimension is connected by the inorganic matter of surface hydroxyl is than the comparative example 2 not carrying out any coating processing and not using table
The mineral-modified gas permeability of the barrier film of comparative example 1 of face hydroxyl and electrochemical stability more preferably, ionic conductivity more
Height, thus the coulombic efficiency first of lithium rechargeable battery is higher, high rate performance and cycle performance more preferably, and lithium ion secondary electricity
The self discharge (i.e. K value) in pond is less.This is because the fibrage of coating can improve the thermal contraction performance of porous substrate, and fiber
Organic fiber can be coupled together, thus ensureing that fibrage has more preferable toughness by the inorganic matter of the surface hydroxyl adding in layer
With intensity so that the loose structure of barrier film is not destroyed, thus conduction in barrier film for the lithium ion can be smoothed out, enter
And can ensure that porous substrate has more preferable air permeability.In the fibrage of the surface of barrier film coating, there is high ionic conductance
Rate, on the one hand can not aoxidized by positive pole with the surface of protective separation film, and on the other hand, this fibrage can be also the conduction of lithium ion
Passage is provided, and in cyclic process, barrier film is played a supporting role, and then be coated with fibrolaminar barrier film and can be lifted
The coulombic efficiency first of lithium rechargeable battery, high rate performance and cycle performance, also can reduce lithium rechargeable battery simultaneously
Self discharge (i.e. K value).Additionally, the interaction between the inorganic matter of surface hydroxyl and organic fiber can be greatly enhanced lithium
Ion is in the intersegmental locomitivity of chain, and then lifts high rate performance and the cycle performance of lithium rechargeable battery.
It can also be seen that the present invention's is coated with fibrage and organic fibre from the contrast of embodiment 1-14 and comparative example 3
The gas permeability of the barrier film that dimension is connected by the inorganic matter of surface hydroxyl is more preferable, electrochemical stability is more preferable, ionic conductivity
Higher, thus the coulombic efficiency first of lithium rechargeable battery is higher, high rate performance and cycle performance more preferably, and lithium ion secondary
The self discharge (i.e. K value) of battery is less.This is because the Fanglun 1414 in comparative example 3 does not have lithium ion
Conducting power, lithium ion will pass through barrier film can only pass through the hole on the fibrage on barrier film surface, thus leading to barrier film
Gas permeability is poor, ionic conductivity is relatively low, and then the high rate performance of lithium rechargeable battery is also poor.
As can be seen that the composition of organic fibre layer can affect from the contrast of embodiment 1, embodiment 6 and embodiment 11-12
The gas permeability of barrier film, when substituent R in monomer 11And R2After bigger molecule substituent group, due to the sterically hindered work of molecule
With increasing so that intermolecular distance increases, therefore the porosity of barrier film becomes big, and gas permeability is improved.
Claims (9)
1. a kind of barrier film of lithium rechargeable battery, including porous substrate it is characterised in that
It is coated with fibrage at least one surface of described porous substrate；
Described fibrage comprises can the organic fiber of conducting lithium ions and the surface hydroxyl connecting described organic fiber
Inorganic matter；
Described organic fiber is selected from homopolymers that monomer 1 formed, is obtained by the aliphatic olefin copolymerization of monomer 1 and C2～C6
One of copolymer and the copolymer that obtained with aromatic olefin copolymerization by monomer 1；
Wherein,
M is selected from one of H, alkali metal and alkaline-earth metal；
R1、R2One of aliphatic group independently selected from H, C1～C6 and aromatic radical.
2. the barrier film of lithium rechargeable battery according to claim 1 is it is characterised in that described fibrolaminar thickness is
1 μm～5 μm, porosity is 10%～80%.
3. lithium rechargeable battery according to claim 1 barrier film it is characterised in that
The quality of described organic fiber is the 65%～99% of described fibrolaminar gross mass；
The quality of the inorganic matter of described surface hydroxyl is the 1%～35% of described fibrolaminar gross mass.
4. the barrier film of lithium rechargeable battery according to claim 1 is it is characterised in that the nothing of described surface hydroxyl
Machine thing is selected from one or more of aerosil, gaseous oxidation aluminium and gaseous oxidation titanium.
5. lithium rechargeable battery according to claim 1 barrier film it is characterised in that
The hydroxy radical content on the surface of inorganic matter of described surface hydroxyl is 100/μm2～1000/μm2；
The specific surface area of the inorganic matter of described surface hydroxyl is 50m2/ g～500m2/g；
The particle diameter of the particle of inorganic matter of described surface hydroxyl is 1nm～1000nm.
6. the barrier film of lithium rechargeable battery according to claim 1 is it is characterised in that described fibrage also comprises to glue
Knot agent, described binding agent is selected from one of polyvinylpyrrolidone, polyvinyl alcohol, Kynoar.
7. lithium rechargeable battery according to claim 6 barrier film it is characterised in that the quality of described binding agent with
The ratio of described fibrolaminar gross mass is more than 0% and is less than or equal to 10%.
8. a kind of preparation method of the barrier film of lithium rechargeable battery, for preparing any one of claim 1-7
The barrier film of lithium rechargeable battery, including step：
(1) dissolve the binder in solvent N-methyl pyrilidone, heat up and stir, obtain binder solution；
(2) add organic fiber in the binder solution of gained, heat up and stir, carry out ultrasonic disperse afterwards, obtain organic
Fiber solution；
(3) add the inorganic matter of surface hydroxyl in the organic fiber solution of gained, be sufficiently stirred for making it be uniformly dispersed, afterwards
Carry out ultrasonic disperse, form organic fibre stuff；
(4) the organic fiber slurry of gained is uniformly coated at least one surface of porous substrate, is dried with baking oven afterwards
Dry dry removing solvent, obtain the barrier film of lithium rechargeable battery, wherein, described organic fiber slurry shape after baking is dried
Become fibrage.
9. a kind of lithium rechargeable battery, including：
Positive plate；
Negative plate；
Barrier film, is interval between positive plate and negative plate；And
Electrolyte；
It is characterized in that, described barrier film is the isolation of the lithium rechargeable battery according to any one of claim 1-7
Film.
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| CN116960574B (en) * | 2023-09-21 | 2024-01-23 | 中材锂膜(南京)有限公司 | Composite coating diaphragm, preparation method thereof and lithium ion battery comprising composite coating diaphragm |
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