CN109428034A - A kind of battery diaphragm and preparation method thereof and lithium ion battery - Google Patents
A kind of battery diaphragm and preparation method thereof and lithium ion battery Download PDFInfo
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- CN109428034A CN109428034A CN201710767069.0A CN201710767069A CN109428034A CN 109428034 A CN109428034 A CN 109428034A CN 201710767069 A CN201710767069 A CN 201710767069A CN 109428034 A CN109428034 A CN 109428034A
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of battery diaphragm and preparation method thereof and include the lithium ion battery of the battery diaphragm, the diaphragm includes porous basement membrane, it is characterized in that, a side surface of the porous basement membrane is attached with rich lithium coating, the richness lithium coating includes first binder and lithium molybdate particle；The lithium ion battery includes the positive electrode, the negative electrode and the separator, and the rich lithium coating of the battery diaphragm is opposite with anode；The present invention forms rich lithium coating by the wherein side in battery diaphragm, and is prepared into battery for the rich lithium coating of the diaphragm is opposite with positive plate, and battery capacity can greatly improve；Diaphragm also has good mechanical performance and high temperature resistance simultaneously.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of battery diaphragm and preparation method thereof and includes the battery
The lithium ion battery of diaphragm.
Background technique
The battery diaphragm of the prior art, which has, forms ceramic diaphragm in the surface coated ceramic coating of polyolefins basement membrane, can be with
Avoiding battery, diaphragm occurs to be heat-shrinked the positive and negative anodes short circuit for leading to battery under high temperature environment, while compared to traditional polyolefin
Class basement membrane, the ceramic diaphragm also can solve the problem of poor diaphragm imbibition rate, bad mechanical property, diaphragm are easily perforated.
Ceramic coating described in the prior art is generally by zirconium oxide, aluminium oxide, silica, titanium oxide, silicon nitride, nitridation
The inorganic oxide particles such as boron and aluminium nitride and binder composition, although optimizing the security performance of battery, with existing
There is the universal of large capacity electric tool, especially electric car is higher and higher to the capacity requirement of battery, therefore how existing
The capacity that battery is further increased on the basis of technology is the hot and difficult issue of existing research.
Summary of the invention
The present invention in view of the above technical problems, proposes a kind of battery diaphragm, including porous basement membrane, the porous basement membrane
One side surface is attached with rich lithium coating, and the richness lithium coating includes first binder and lithium molybdate particle.
Present inventor has been surprisingly found that in test, contains molybdenum in the opposite side surface attachment of battery diaphragm and anode
The rich lithium coating of sour lithium particle, can greatly improve the capacity of battery, inventor's conjecture, and lithium molybdate particle of the invention can supplement
Battery electrode especially cathode because caused by forming SEI film lithium lose, can greatly improve the capacity of battery, but lithium molybdate particle
Presence will not influence the mechanical performance and high temperature resistance of existing diaphragm.
The invention also provides the preparation method of above-mentioned battery diaphragm, this method includes by first binder, lithium molybdate
Grain and organic solvent are mixed to get slurry, and slurry is attached to a side surface of porous basement membrane, is then dried.
Present invention further propose that a kind of lithium ion battery, including anode, cathode and between anode and cathode every
Film, the diaphragm is battery diaphragm proposed by the present invention, and the rich lithium coating of the battery diaphragm is opposite with anode.
Specific embodiment
In order to which the technical problems, technical solutions and beneficial effects solved by the present invention is more clearly understood, below in conjunction with
Specific embodiment, the present invention is further described in detail, it should be understood that specific embodiment described herein is only used for
It explains the present invention, is not intended to limit the present invention.
The present invention provides a kind of battery diaphragm, including porous basement membrane, a side surface of the porous basement membrane is attached with richness
Lithium coating, the richness lithium coating includes first binder and lithium molybdate particle.
The battery diaphragm provided according to the present invention, it is preferable that on the basis of the gross mass of the rich lithium coating, the molybdic acid
The content of lithium particle is 5%-97%, and the content of the first binder is 3%-15%；It is further preferred that with the rich lithium coating
Gross mass on the basis of, the content of the lithium molybdate particle is 85%-97%, and the content of the first binder is 3%-5%；This Shen
Inventor please is by further experiment discovery, when the content of lithium molybdate particle accounts for the 85%-97% of rich lithium coating gross mass
, while the battery diaphragm being prepared is with optimal mechanical performance and high temperature resistance also there is optimal cathode to mend lithium
Effect.
The battery diaphragm provided according to the present invention, it is preferable that the richness lithium coating further includes the first inorganic oxide particles,
On the basis of the gross mass of the rich lithium coating, the content of first inorganic oxide particles is 92% or less；Further preferably
Ground, on the basis of the gross mass of the rich lithium coating, the content of first inorganic oxide particles is 10% or less；By rich lithium
When the additive amount of the first inorganic oxide particles in coating is controlled below 10%, the battery diaphragm being prepared has optimal
Mechanical performance and high temperature resistance while also there is optimal charge-discharge performance.
The battery diaphragm provided according to the present invention, it is preferable that another side surface of the porous basement membrane is attached with ceramic painting
Layer, the ceramic coating include the second inorganic oxide particles and the second binder；In above-mentioned ceramic coating, described second is inorganic
The type of oxide particle and the second binder and content are well known to the technical staff of ceramic diaphragm field, and therefore not to repeat here.
The battery diaphragm provided according to the present invention, it is preferable that the average grain diameter of the lithium molybdate particle is 50-500nm；This
The inventor of application is by further experiment discovery, when the average grain diameter of lithium molybdate particle controls between 50-500nm,
Battery capacity is compared with using the battery of conventional ceramic diaphragm to can be improved 3% or so, and when the control of the average grain diameter of lithium molybdate particle exists
When between 100-300nm, battery capacity can be improved 4% or so compared with using the battery of conventional ceramic diaphragm；Therefore, work as lithium molybdate
When the average grain diameter of particle is between herein described value, which there is optimal cathode to mend lithium effect.
The battery diaphragm provided according to the present invention, it is preferable that first inorganic oxide particles and the second inorganic oxide
Composition granule can be the same or different, separately selected from aluminum oxide, titanium dioxide, silica, zirconium dioxide,
Stannic oxide, magnesia, zinc oxide, aluminium nitride, magnesium nitride, barium carbonate, barium sulfate, one of barium titanate and calcium sulfate or more
Kind；The first binder and the second binder can be the same or different, and separately be selected from Kynoar, butylbenzene
One of rubber, epoxy resin, polytetrafluoroethylene (PTFE), polyacrylamide, polyvinyl alcohol, polyethylene glycol and polyethylene glycol oxide are more
Kind.
The battery diaphragm provided according to the present invention, it is preferable that it is described richness lithium coating with a thickness of 0.5 ~ 5 μm, preferably 1 ~ 2
μm。
The present invention also provides a kind of preparation method of battery diaphragm, the method includes by first binder, lithium molybdate
Particle and organic solvent are mixed to get slurry, and slurry is attached to a side surface of porous basement membrane, is then dried；Specifically,
The preparation method of the battery diaphragm includes by first binder, lithium molybdate particle and organic solvent 500-3000rpm's
It is uniformly mixed to obtain slurry under revolving speed, then obtained slurry is coated on a side surface of porous basement membrane, is then dried
It does to form rich lithium coating on a side surface of the porous basement membrane；The battery diaphragm side being prepared at this time is attached with richness
Lithium coating, the other side are porous membrane surface.
In the application, the preparation method of the battery diaphragm can also be first binder, lithium molybdate particle and have
Solvent is uniformly mixed and obtains slurry, slurry is coated in a side surface of porous basement membrane, then separately by the second inorganic oxide
Particle, the second binder and solvent are uniformly mixed and obtain ceramic slurry, and ceramic slurry is coated in the other side of porous basement membrane
Then surface is dried, battery diaphragm is prepared；The diaphragm side being prepared at this time is attached with rich lithium coating, and the other side is attached
Have ceramic coating.
Organic solvent used in above-mentioned preparation richness lithium coating with prepare solvent used in ceramic coating can be identical
Can be different, separately it is selected from N-Methyl pyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide, four
One of hydrogen furans, water and ethyl alcohol are a variety of.
In the slurry for preparing rich lithium coating, on the basis of the gross mass of the rich lithium coating, the lithium molybdate particle
Content is 5%-97%, and the content of the first binder is 3%-15%；The content of the organic solvent is 50%-1000%；Into one
It walks preferably, in the slurry for preparing rich lithium coating, on the basis of the gross mass of the rich lithium coating, the lithium molybdate particle
Content is 85%-97%, and the content of the first binder is 3%-%, and the content of the organic solvent is 50%-100%.
The battery diaphragm provided according to the present invention, it is preferable that in the slurry for preparing rich lithium coating, first can also be added
Inorganic oxide particles, the content of first inorganic oxide particles are 92% hereinafter, preferably 10% or less.
In the application, preparing for ceramic coating is known to those skilled in the art, and therefore not to repeat here.
The preparation method of the battery diaphragm provided according to the present invention, the thickness of the porous basement membrane typically 5-30 μ
M, preferably 6-25 μm；, wherein porous basement membrane is polymer porous film or non-woven fabrics, the material of the porous basement membrane can be selected from
Polyethylene glycol oxide, polyacrylonitrile, Kynoar, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol, polyamide, poly- pair
One of ethylene terephthalate, polyethylene, polypropylene and its derivative are a variety of；Preferably, the porous basement membrane is
MIcroporous polyolefin film, wherein MIcroporous polyolefin film can be PP/PE/PP trilamellar membrane, PP/PP duplicature, PE/PE duplicature, PP/
Any one in PE duplicature, PP monofilm or PE monofilm.
The preparation method of the battery diaphragm provided according to the present invention, it is preferable that the organic solvent is selected from N- methylpyrrole
One of alkanone, dimethylformamide, diethylformamide, dimethyl sulfoxide, tetrahydrofuran, water and ethyl alcohol are a variety of；
Present inventor is had found by test of many times, using above-mentioned organic solvent, enables to make pottery when preparing ceramic layer slurry
Porcelain particle and lithium molybdate particle reach good dispersion effect.
The present invention also provides a kind of lithium ion battery, the lithium ion battery include anode, cathode and be located at anode and
Diaphragm between cathode, wherein the diaphragm is above-mentioned battery diaphragm provided by the invention, and the rich lithium coating of the battery diaphragm
It is opposite with anode.
Lithium ion battery provided by the invention, structure and preparation method are known to those skilled in the art；The present invention
The lithium ion battery of offer comprising shell, positioned at the pole piece of enclosure interior, the cover board of seal casinghousing and be located at enclosure interior at
Electrolyte between pole piece；The pole piece includes positive and negative plate and the diaphragm between positive and negative plate；Wherein, positive and negative
Pole piece is the positive and negative plate of this field routine, and electrolyte is the nonaqueous electrolytic solution of this field routine, is not repeated herein；Every
Film is above-mentioned battery diaphragm provided by the present application.
The preparation method of lithium ion battery of the invention is known to the skilled person, including by anode, battery diaphragm
Pole piece is stacked gradually or is wound into cathode, wherein only should be noted the rich lithium coating of battery diaphragm and anode relatively, so
Electrolyte is injected into the pole piece afterwards and is sealed, wherein the diaphragm is above-mentioned battery diaphragm provided by the present application.
The present invention is further detailed below by specific embodiment.
Embodiment 1
(1) preparation of battery diaphragm
By the Kynoar and 5 parts by weight of the lithium molybdate particle (average grain diameter 200nm) of 91 parts by weight and 4 parts by weight
Alumina particle is added in the N-Methyl pyrrolidone of 50 parts by weight, obtains slurry with the revolving speed stirring 10min of 1000rpm, will
The slurry is coated on a side surface of polyethylene based film, and dry 4h at 60 DEG C obtains the side surface attachment of polyethylene based film
Have a battery diaphragm C1 of rich lithium coating, polyethylene based film with a thickness of 10 μm, rich lithium coating with a thickness of 2 μm；
(2) preparation of battery
Weigh LiFePO4 (LiFePO4), acetylene black, polyvinylidene fluoride (PVDF), N-Methyl pyrrolidone (NMP) according to weight
Amount compares LiFePO4: acetylene black: PVDF:NMP=85:10:5:50 prepares anode sizing agent, and coating machine is coated in 12 μm after mixing evenly
On thick aluminium foil, then in 120 DEG C of dry 5h in vacuum environment, tabletting machine is then used, is finally sliced, grown × wide
× thickness=551mm × 44mm × 130 μm lithium ion cell positive；Graphite, polyvinylidene fluoride are weighed according to weight ratio graphite:
PVDF=100:3 prepares negative electrode slurry, and coating machine is coated on the copper foil of 8 μ m-thicks after mixing evenly, then dries at 80 DEG C for 24 hours,
Then tabletting machine is used, is finally sliced, is grown × width x thickness=551mm × 44mm × 130 μm negative electrode of lithium ion battery；
The rich lithium coating face anode for the battery diaphragm being prepared in step (1) is placed, the side face of uncoated richness lithium coating
Cathode is placed, and assembling obtains lithium ion battery, is then injected into nonaqueous electrolytic solution, lithium-ion electric is made in finally sealed battery case
Pond sample S1；Wherein electrolyte is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixing
Solution (volume ratio is=1: 1)；The assembling process of battery carries out in the glove box full of argon gas；Lithium-ion electric is prepared
Pond S1.
Embodiment 2
Battery diaphragm and battery are prepared using method same as Example 1, unlike, the step of preparing battery diaphragm
(1) in, the lithium molybdate particle of addition is 93 parts by weight, and alumina particle is 3 parts by weight, and the average grain diameter of lithium molybdate particle is
300nm；Battery diaphragm C2 and lithium ion battery S2 is prepared.
Embodiment 3
Battery diaphragm and battery are prepared using method same as Example 1, unlike, the step of preparing battery diaphragm
(1) in, the lithium molybdate particle of addition is 95 parts by weight, and alumina particle is 1 parts by weight, and the average grain diameter of lithium molybdate particle is
100nm；Battery diaphragm C3 and lithium ion battery S3 is prepared.
Embodiment 4
(1) preparation of battery diaphragm
50 parts by weight are added in the lithium molybdate particle (average grain diameter 200nm) of 97 parts by weight and the Kynoar of 3 parts by weight
N-Methyl pyrrolidone in, slurry is obtained with the revolving speed of 1500rpm stirring 10min, which is coated in polyethylene based film
A side surface on, the alumina particle of 97 parts by weight and the Kynoar of 3 parts by weight are separately added to the N- first of 50 parts by weight
In base pyrrolidones, ceramic slurry is obtained with the revolving speed stirring 10min of 1500rpm, which is coated in polyvinyl
On another side surface of film, the dry 4h at 60 DEG C, the side surface for obtaining polyethylene based film is attached with rich lithium coating and another
One side surface is attached with the battery diaphragm C4 of ceramic coating, polyethylene based film with a thickness of 10 μm, rich lithium coating with a thickness of 2 μ
m；Ceramic layer with a thickness of 2 μm；
(2) preparation of battery
By the rich lithium coating of the above-mentioned battery diaphragm being prepared and positive relative makeup battery, other conditions and 1 phase of embodiment
Together, lithium ion battery S4 is prepared.
Embodiment 5
Battery diaphragm and lithium ion battery are prepared using method same as Example 1, unlike, rich lithium coating with a thickness of
0.5 μm, battery diaphragm C5 and lithium ion battery S5 is prepared.
Embodiment 6
Battery diaphragm and lithium ion battery are prepared using method same as Example 1, unlike, rich lithium coating with a thickness of
5 μm, battery diaphragm C6 and lithium ion battery S6 is prepared.
Embodiment 7
50 parts by weight are added in the lithium molybdate particle (average grain diameter 500nm) of 97 parts by weight and the Kynoar of 3 parts by weight
N-Methyl pyrrolidone in, slurry is obtained with the revolving speed of 2000rpm stirring 10min, which is coated in polyethylene based film
A side surface on, dry 4h, the side surface for obtaining polyethylene based film are attached with the battery diaphragm C7 of rich lithium coating at 60 DEG C,
Polyethylene based film with a thickness of 10 μm, rich lithium coating with a thickness of 2 μm；
(2) preparation of battery
Weigh LiFePO4 (LiFePO4), acetylene black, polyvinylidene fluoride (PVDF), N-Methyl pyrrolidone (NMP) according to weight
Amount compares LiFePO4: acetylene black: PVDF:NMP=85:10:5:50 prepares anode sizing agent, and coating machine is coated in 12 μm after mixing evenly
On thick aluminium foil, then 120 DEG C of dry 5h, then use tabletting machine, are finally sliced, grown × width x thickness=551mm ×
The lithium ion cell positive of 44mm × 130 μm；Graphite, polyvinylidene fluoride are weighed according to weight ratio graphite: PVDF=100:3 matches
Negative electrode slurry processed, coating machine is coated on the copper foil of 8 μ m-thicks after mixing evenly, and then drying for 24 hours, then uses pressure at 80 DEG C of temperature
Piece machine tabletting, is finally sliced, and is grown × width x thickness=551mm × 44mm × 130 μm negative electrode of lithium ion battery；By step (1)
In the rich lithium coating face anode of battery diaphragm that is prepared place, the side face cathode of uncoated ceramic layer is placed, group
Dress obtains lithium ion battery, is then injected into nonaqueous electrolytic solution, lithium ion battery sample S7 is made in finally sealed battery case；Its
Middle electrolyte is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed solution (volume ratio
For=1: 1)；The assembling process of battery carries out in the glove box full of argon gas；Lithium ion battery S7 is prepared.
Embodiment 8
By the lithium molybdate particle (average grain diameter 50nm) of 97 parts by weight and the Kynoar of 3 parts by weight 50 parts by weight are added
N-Methyl pyrrolidone in, slurry is obtained with the revolving speed of 3000rpm stirring 10min, which is coated in polyethylene based film
A side surface on, the titanium dioxide of 97 parts by weight and the Kynoar of 3 parts by weight are added to the N- methyl pyrrole of 50 parts by weight
In pyrrolidone, ceramic slurry is obtained with the revolving speed stirring 10min of 500rpm, which is coated in the another of polyethylene based film
On one side surface, the dry 4h at 60 DEG C, the side surface for obtaining polyethylene based film is attached with rich lithium coating and other side table
Face is attached with the battery diaphragm C8 of ceramic coating, polyethylene based film with a thickness of 10 μm, rich lithium coating with a thickness of 2 μm；Ceramics
Coating with a thickness of 2 μm；
(2) preparation of battery
By the rich lithium coating of the above-mentioned battery diaphragm being prepared and positive relative makeup battery, other conditions and 4 phase of embodiment
Together, lithium ion battery S8 is prepared.
Embodiment 9
(1) preparation of battery diaphragm
By the Kynoar and 10 parts by weight of the lithium molybdate particle (average grain diameter 200nm) of 85 parts by weight and 5 parts by weight
Alumina particle be added in the N-Methyl pyrrolidone of 50 parts by weight, slurry is obtained with the revolving speed of 500rpm stirring 10min, will
The slurry is coated on a side surface of polyethylene based film, and dry 4h at 60 DEG C obtains the side surface attachment of polyethylene based film
Have a battery diaphragm C9 of rich lithium coating, polyethylene based film with a thickness of 10 μm, rich lithium coating with a thickness of 2 μm；
(2) preparation of battery
Weigh LiFePO4 (LiFePO4), acetylene black, polyvinylidene fluoride (PVDF), N-Methyl pyrrolidone (NMP) according to weight
Amount compares LiFePO4: acetylene black: PVDF:NMP=85:10:5:50 prepares anode sizing agent, and coating machine is coated in 12 μm after mixing evenly
On thick aluminium foil, then 120 DEG C of dry 5h, then use tabletting machine, are finally sliced, grown × width x thickness=551mm ×
The lithium ion cell positive of 44mm × 130 μm；Graphite, polyvinylidene fluoride are weighed according to weight ratio graphite: PVDF=100:3 matches
Negative electrode slurry processed, coating machine is coated on the copper foil of 8 μ m-thicks after mixing evenly, and then drying for 24 hours, then uses pressure at 80 DEG C of temperature
Piece machine tabletting, is finally sliced, and is grown × width x thickness=551mm × 44mm × 130 μm negative electrode of lithium ion battery；By step (1)
In the rich lithium coating face anode of battery diaphragm that is prepared place, the side face cathode of uncoated richness lithium coating is placed,
Assembling obtains lithium ion battery, is then injected into nonaqueous electrolytic solution, lithium ion battery sample S9 is made in finally sealed battery case；
Wherein electrolyte is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbonate (DMC) mixed solution (volume
Than for=1: 1)；The assembling process of battery carries out in the glove box full of argon gas；Lithium ion battery S9 is prepared.
Embodiment 10
Battery diaphragm and lithium ion battery are prepared using method same as Example 1, unlike, in step (1), add
The lithium molybdate particle entered is 5 parts by weight, and Kynoar is 3 parts by weight, and alumina particle is 92 parts by weight, and battery is prepared
Diaphragm C10 and lithium ion battery S10.
Comparative example 1
(1) preparation of battery diaphragm
By in the N-Methyl pyrrolidone of 50 parts by weight of the alumina particle of 93 parts by weight and the Kynoar of 3 parts by weight, with
The revolving speed stirring 10min of 1000rpm obtains ceramic slurries, which is coated in the both side surface of polyethylene based film,
Dry 4h at 60 DEG C, obtains poly- battery diaphragm DC1, polyethylene based film with a thickness of 10 μm, single side ceramic coating with a thickness of 2 μ
m；
(2) preparation of battery
Preparing for battery is same as Example 1, unlike the diaphragm that uses in battery for the battery that does not add lithium molybdate particle
Lithium ion battery DS1 is prepared in diaphragm.
Comparative example 2
Battery diaphragm and lithium ion battery are prepared using method same as Example 1, unlike, lithium molybdate particle is using same
The lithium manganese phosphate particle of parts by weight replaces, and battery diaphragm DC2 and lithium ion battery DS2 is prepared.
Comparative example 3
(1) preparation of battery diaphragm
By in the N-Methyl pyrrolidone of 50 parts by weight of the alumina particle of 93 parts by weight and the Kynoar of 3 parts by weight, with
The revolving speed stirring 10min of 1000rpm obtains ceramic slurries, which is coated on a side surface of polyethylene based film,
Dry 4h at 60 DEG C, obtains poly- battery diaphragm DC3, polyethylene based film with a thickness of 10 μm, ceramic layer with a thickness of 2 μm；
(2) preparation of battery
Preparing for battery is same as Example 1, the difference is that the diaphragm DC3 coated ceramic that will be prepared in above-mentioned steps (1)
One side and positive relative makeup battery, other steps and technique are all the same, and lithium ion battery DS3 is prepared.
Performance test
(1) tensile property is tested
The battery diaphragm sample that 4mm × 50mm is intercepted from diaphragm C1-C9 and DC1-DC3, utilizes universal electrical testing machine WDW-
0.5 carries out tension test, and power size N when record diaphragm sample is broken calculates the cross section S of diaphragm, counted by formula N/S
The tensile strength of diaphragm sample is calculated, test result is recorded in table 1.
(2) puncture resistance is tested
The battery diaphragm sample that 70mm × 70mm is intercepted from diaphragm C1-C9 and DC1-DC3, utilizes universal electrical testing machine WDW-
0.5 carries out puncture test, and test result is recorded in table 1.
(3) peel strength test
The battery diaphragm sample that 40mm × 100mm is intercepted from diaphragm C1-C9 and DC1-DC3, with adhesive tape battery diaphragm two sides
It is separately fixed on stationary fixture and floating holder, 180 DEG C of negative drawings make ceramic layer and substrate film stripping, and required pulling force is got over
Greatly, then the peel strength of battery diaphragm is better, and acquired results are as shown in table 1.
(4) permeability test
13cm is intercepted from diaphragm C1-C9 and DC1-DC32The battery diaphragm sample of area utilizes grignard value tester GURLEY-
4110, pressure (water column is high) 12.39cm, measurement 100ml gas (air) is through the time required for aforementioned battery diaphragm sample
(s/100ml), numerical value is smaller, shows that its gas permeability is better.Acquired results are as shown in table 1.
(5) thermal contraction performance is tested
Each 2 parts of battery diaphragm sample of 50mm × 50mm are intercepted from diaphragm C1-C9 and DC1-DC3, are respectively placed in 90 DEG C of bakings
Toasted 2 hours in case and 120 DEG C of baking ovens in toast 1 hour, the long L of rapid measuring diaphragm, wide W are taken out after baking immediately.It is sharp again
With formula: shrinking percentage η=(S0-S1)/S0=(1-LW/2500) × 100% is calculated, wherein S1For toast metacneme area,
S0For the diaphragm area of cutting.Acquired results are as shown in table 1.
(6) charge/discharge capacity is tested
Battery sample S1-S9 and DS1-DS3 is taken to test charging capacity and electric discharge in charge-discharge test instrument LAND-CT2001A
Capacity first charges to 4.3V under the multiplying power of 0.1C, and standing is discharged to 2.75V under 0.1C multiplying power after five minutes, and record is first respectively
Test result is recorded in table 2 by secondary charging capacity and discharge capacity.
Table 1
Table 2
Lithium molybdate, and the one of diaphragm particle containing lithium molybdate are coated in membrane surface it can be seen from the test result of Tables 1 and 2
Side is corresponding with anode to be assembled into lithium ion battery, and the charge/discharge capacity of battery significantly improves, and diaphragm still have it is good
Good mechanical performance and heat resistance, thus illustrate that battery diaphragm provided by the present application is applied to battery, in battery charging process
In, the lithium molybdate particle in rich lithium coating also takes off lithium for cathode and provides capacity, has the effect of that cathode mends lithium.
Claims (13)
1. a kind of battery diaphragm, including porous basement membrane, which is characterized in that a side surface of the porous basement membrane is attached with rich lithium and applies
Layer, the richness lithium coating includes first binder and lithium molybdate particle.
2. battery diaphragm according to claim 1, which is characterized in that on the basis of the gross mass of the rich lithium coating, institute
The content for stating lithium molybdate particle is 5%-97%, and the content of the first binder is 3%-15%.
3. battery diaphragm according to claim 2, which is characterized in that on the basis of the gross mass of the rich lithium coating, institute
The content for stating lithium molybdate particle is 85%-97%, and the content of the first binder is 3%-5%.
4. battery diaphragm according to claim 1, which is characterized in that the richness lithium coating further includes the first inorganic oxide
Particle, on the basis of the gross mass of the rich lithium coating, the content of first inorganic oxide particles is 92% or less.
5. battery diaphragm according to claim 4, which is characterized in that on the basis of the gross mass of the rich lithium coating, institute
The content for stating the first inorganic oxide particles is 10% or less.
6. according to battery diaphragm described in claim 4-5 any one, which is characterized in that the other side table of the porous basement membrane
Face is attached with ceramic coating, and the ceramic coating includes the second inorganic oxide particles and the second binder.
7. battery diaphragm described in -5 any one according to claim 1, which is characterized in that the average grain of the lithium molybdate particle
Diameter is 50-500nm.
8. battery diaphragm according to claim 7, which is characterized in that the average grain diameter of the lithium molybdate particle is 100-
300nm。
9. battery diaphragm according to claim 6, which is characterized in that first inorganic oxide particles and second inorganic
Oxide particle can be the same or different, and separately be selected from aluminum oxide, titanium dioxide, silica, dioxy
Change zirconium, stannic oxide, magnesia, zinc oxide, aluminium nitride, magnesium nitride, barium carbonate, barium sulfate, one in barium titanate and calcium sulfate
Kind is a variety of；The first binder and the second binder can be the same or different, and separately be selected from polyvinylidene fluoride
In alkene, butadiene-styrene rubber, epoxy resin, polytetrafluoroethylene (PTFE), polyacrylamide, polyvinyl alcohol, polyethylene glycol and polyethylene glycol oxide
It is one or more.
10. battery diaphragm described in -5 any one according to claim 1, which is characterized in that it is described richness lithium coating with a thickness of
0.5~5μm。
11. a kind of preparation method of battery diaphragm, the method includes by first binder and lithium molybdate particle with it is organic molten
Agent is mixed to get slurry, and slurry is attached to a side surface of porous basement membrane, is then dried.
12. the preparation method of battery diaphragm according to claim 11, which is characterized in that the organic solvent is selected from N- first
One of base pyrrolidones, dimethylformamide, diethylformamide, dimethyl sulfoxide, tetrahydrofuran, water and ethyl alcohol or
It is a variety of.
13. a kind of lithium ion battery, including anode, cathode and the diaphragm between anode and cathode, which is characterized in that described
Diaphragm is battery diaphragm described in claim 1-10 any one, and the rich lithium coating of the battery diaphragm is opposite with anode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463414A (en) * | 2020-04-09 | 2020-07-28 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
| CN111900315A (en) * | 2020-08-04 | 2020-11-06 | 中国科学院物理研究所 | Ceramic diaphragm with double-sided coating material coating and preparation method and application thereof |
| CN115051109A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium-supplementing composite isolating membrane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150214543A1 (en) * | 2014-01-27 | 2015-07-30 | Samsung Sdi Co., Ltd. | Positive active material, lithium battery including the same, and method of manufacturing the positive active material |
| CN106784614A (en) * | 2017-03-22 | 2017-05-31 | 江苏元景锂粉工业有限公司 | A kind of high security lithium ion battery and preparation method thereof |
| CN106876633A (en) * | 2017-02-22 | 2017-06-20 | 北京卫蓝新能源科技有限公司 | A kind of composite diaphragm, lithium battery and preparation method thereof |
-
2017
- 2017-08-31 CN CN201710767069.0A patent/CN109428034A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150214543A1 (en) * | 2014-01-27 | 2015-07-30 | Samsung Sdi Co., Ltd. | Positive active material, lithium battery including the same, and method of manufacturing the positive active material |
| CN106876633A (en) * | 2017-02-22 | 2017-06-20 | 北京卫蓝新能源科技有限公司 | A kind of composite diaphragm, lithium battery and preparation method thereof |
| CN106784614A (en) * | 2017-03-22 | 2017-05-31 | 江苏元景锂粉工业有限公司 | A kind of high security lithium ion battery and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463414A (en) * | 2020-04-09 | 2020-07-28 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
| CN111463414B (en) * | 2020-04-09 | 2021-06-15 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Interlayer material and preparation method and application thereof |
| CN111900315A (en) * | 2020-08-04 | 2020-11-06 | 中国科学院物理研究所 | Ceramic diaphragm with double-sided coating material coating and preparation method and application thereof |
| CN111900315B (en) * | 2020-08-04 | 2021-10-22 | 中国科学院物理研究所 | Ceramic diaphragm with double-sided coating material coating and preparation method and application thereof |
| CN115051109A (en) * | 2022-06-28 | 2022-09-13 | 楚能新能源股份有限公司 | Lithium-supplementing composite isolating membrane and preparation method and application thereof |
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Application publication date: 20190305 |