CN109167013A - Coating fluid, lithium ion battery separator and lithium ion battery for lithium ion battery - Google Patents

Coating fluid, lithium ion battery separator and lithium ion battery for lithium ion battery Download PDF

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Publication number
CN109167013A
CN109167013A CN201811014090.4A CN201811014090A CN109167013A CN 109167013 A CN109167013 A CN 109167013A CN 201811014090 A CN201811014090 A CN 201811014090A CN 109167013 A CN109167013 A CN 109167013A
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CN
China
Prior art keywords
ion battery
lithium ion
coating
nano
battery separator
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Pending
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CN201811014090.4A
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Chinese (zh)
Inventor
王艳杰
伍志杰
陈莉
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Shenzhen Senior Technology Material Co Ltd
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Shenzhen Senior Technology Material Co Ltd
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Application filed by Shenzhen Senior Technology Material Co Ltd filed Critical Shenzhen Senior Technology Material Co Ltd
Priority to CN201811014090.4A priority Critical patent/CN109167013A/en
Publication of CN109167013A publication Critical patent/CN109167013A/en
Priority to US17/255,809 priority patent/US20210280947A1/en
Priority to JP2020567128A priority patent/JP7202400B2/en
Priority to PCT/CN2019/088088 priority patent/WO2020042684A1/en
Priority to KR1020207036390A priority patent/KR102507794B1/en
Priority to EP19855799.3A priority patent/EP3846245A4/en
Pending legal-status Critical Current

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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/446Composite material consisting of a mixture of organic and inorganic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/411Organic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/431Inorganic material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of coating fluid of lithium ion battery separator, lithium ion battery separator and lithium ion battery, the raw material of the coating fluid includes: nano wire, polymer particles, adhesive and solvent;The nano wire is at least one of nano-cellulose, carbon nanotube, nano-silver thread, boron carbide nano wires, Kocide SD nano wire, aramid nano-fiber, silicon monoxide nano wire and hydroxyapatite nano line;The polymer particles are at least one of polyoxyethylene, polypropylene oxide, polyetherimide, Kynoar, polyacrylonitrile, polymethyl methacrylate, Kynoar hexafluoropropene and aramid fiber.The present invention will be mixed to get the surface that coating fluid is coated on septum body using nano wire, polymer particles and adhesive etc., and solidify, it obtains by septum body and the coat composed lithium ion battery separator being supported in the septum body, which has good thermal stability and preferable adhesive property etc..

Description

Coating fluid, lithium ion battery separator and lithium ion battery for lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of coating fluid for lithium ion battery, Lithium ion battery separator and lithium ion battery.
Background technique
Lithium ion battery due to specific energy is big, operating voltage is high, service life cycle is long, memory-less effect, self discharge are small, Pollution free green environment protection, the advantages that having extended cycle life, have been widely used in Portable mobile electronic device such as mobile phone, have taken the photograph Camera, laptop etc. are also listed in the candidate power supply of electric car, space flight, military affairs and large-scale energy storage device.With lithium from The development of sub- battery, requires the capacity, high and low temperature resistance and cycle life etc. of battery higher and higher, and lithium ion battery is one Kind uses extensive secondary cell at present.
Lithium ion battery is mainly made of four big materials, including positive electrode, negative electrode material, diaphragm, electrolyte.As it One of important component part, diaphragm play the role of its performance considerable.Diaphragm (battery separator) refers to One layer of diaphragm material between the anode and cathode of battery, is usually referred to as with battery diaphragm.The main function of battery diaphragm is: Isolation positive and negative electrode simultaneously prevent the electronics in battery from passing freely through, while allow the ion in electrolyte between positive and negative anodes from By passing through.
The ionic conductivity of battery diaphragm is directly related to the overall performance of battery.Its effect that positive and negative anodes are isolated makes electricity Pond can limit the rise of current in the case of overcharging or temperature rise, prevent battery short circuit from causing explosion, and have micro- The self-closing protective effect in hole, plays the role of safeguard protection to battery user and equipment.
Since polyolefine material is cheap, and have preferable mechanical strength and chemical stability, comprehensive performance it is good, at This it is cheap the advantages that and be widely used as micro-pore septum.But since that there are thermal stability is poor for it, and its with electrode adhesion Difference and the relatively soft problem of battery for leading to assembling, therefore limit its further applying in the battery.
Summary of the invention
In view of this, a kind of coating fluid, lithium ion battery separator and lithium for lithium ion battery provided by the invention from Sub- battery, preferably overcomes the above-mentioned problems of the prior art and defect, and the present invention will use nano wire, polymer particles And adhesive etc. is mixed to get the surface that coating fluid is coated on septum body, and solidifies, and obtains by septum body and is supported on institute The coat composed lithium ion battery separator in septum body is stated, which has good thermal stability and machine Tool intensity, and there is preferable caking property, keep it good with the caking property of electrode, efficiently solving existing diaphragm, there are thermostabilizations Property it is poor, and its with electrode adhesion difference and lead to the relatively soft problem of battery of assembling.
A kind of coating fluid for lithium ion battery separator, the raw material of the coating fluid include: that nano wire, polymer are micro- Grain, adhesive and solvent;
The nano wire be nano-cellulose, carbon nanotube, nano-silver thread, boron carbide nano wires, Kocide SD nano wire, At least one of aramid nano-fiber, silicon monoxide nano wire and hydroxyapatite nano line;The diameter of the nano wire is 1 ~100nm, length are 0.1~100 μm;
The polymer particles are polyoxyethylene, polypropylene oxide, polyetherimide, Kynoar, polyacrylonitrile, gather At least one of methyl methacrylate, Kynoar hexafluoropropene and aramid fiber, the partial size of the polymer particles are 50 ~10000nm.
Further, the mass ratio of the polymer particles and the nano wire is (0.1~5): 1;The nano wire Quality accounts for the 1~30% of the quality of the solvent;The quality of the adhesive accounts for the 1~50% of the quality of the solvent.
Further, the raw material of the coating fluid further include: auxiliary agent;The quality of the auxiliary agent accounts for the quality of the solvent 0.01~3%
Further, the adhesive is polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, butadiene-styrene rubber, carboxymethyl cellulose At least one of element, Kynoar, polyvinylpyrrolidone and polyimides;The solvent include water, ethyl alcohol, acetone and At least one of N-Methyl pyrrolidone.
Further, the auxiliary agent be fluoro-alkyl ethyoxyl alcohol ether, fatty alcohol polyoxyethylene ether, butylbenzene sodium naphthalene sulfonate, At least one of ethylene hydroxy sulfuric acid sodium and lauryl sodium sulfate.
The present invention also provides a kind of lithium ion battery separators, including septum body and are supported in the septum body Coating, the coating are obtained using above-mentioned coating fluid in an at least side surface for the septum body coating, solidification.
Further, the mode of the coating is dip-coating, spraying, spin coating or blade coating.
Further, the septum body is microporous polypropylene membrane, polyethene microporous membrane or polypropylene, polyethylene micropore Film;3~20 μm of the thickness of the septum body.
Further, the coating with a thickness of 0.01~1 μm.
The present invention also provides a kind of lithium ion battery of profit, the lithium ion battery include above-mentioned lithium ion battery every Film.
Compared with prior art, a kind of coating fluid, lithium ion battery separator and lithium for lithium ion battery of the invention The beneficial effect of ion battery is:
The present invention will be mixed to get coating fluid using nano wire, polymer particles and adhesive etc. and be coated on septum body Surface, and solidify, it obtains by septum body and the coat composed lithium ion battery separator being supported in the septum body, it should Lithium ion battery separator has good thermal stability and mechanical strength, and has preferable caking property, keeps it viscous with electrode Knot property is good, efficiently solves existing diaphragm there are thermal stability is poor, and its with electrode adhesion difference and lead to the battery of assembling Relatively soft problem;Further, nano wire and polymer particles that the coating material of the lithium ion battery separator uses, can be with Avoid the problem that coating is thicker and the thickness of entire diaphragm and weight is caused to increase, so that it is steady to have reached lithium ion battery separator heat Qualitative good, thickness and weight increase small effect.
To enable the above objects, features and advantages of the present invention to be clearer and more comprehensible, preferred embodiment is cited below particularly, makees detailed It is described as follows.
Specific embodiment
To facilitate the understanding of the present invention, it elaborates below with reference to the mode of embodiment to technical solution of the present invention, In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technologies used herein and scientific term have and the common skill of fields of the present invention The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
Term as used herein:
" by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " Or its any other deformation, it is intended that cover non-exclusionism includes.For example, composition, step, method comprising listed elements, Product or device are not necessarily limited to those elements, but may include not expressly listed other elements or such composition, step Suddenly, method, product or the intrinsic element of device.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim, This phrase will make claim closed, so that it is not included the material in addition to the material of those descriptions, but relative Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after When, only it is limited to element described in the clause;Other elements be not excluded the claim as a whole it Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~ 5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A And B) and (A or B).
A kind of coating fluid for lithium ion battery separator, the raw material of the coating fluid include: that nano wire, polymer are micro- Grain, adhesive and solvent.
It should be noted that the draw ratio (i.e. the ratio of length and diameter) of the nano wire need to be greater than 50, such as nanometer The draw ratio of line can be 100,500,1000,8000 or 10000 etc.;The diameter of the nano wire be 1~100nm such as 1nm, 5nm, 10nm, 20nm, 30nm, 50nm, 80nm or 100nm etc.;The length of the nano wire is 0.1~100 μm such as 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 30 μm, 50 μm, 80 μm or 100 μm etc..
The nano wire be nano-cellulose, carbon nanotube, nano-silver thread, boron carbide nano wires, Kocide SD nano wire, At least one of aramid nano-fiber, silicon monoxide nano wire and hydroxyapatite nano line.
The polymer particles are polyoxyethylene (PEO), polypropylene oxide (PPO), polyetherimide (PEI), gather inclined fluorine Ethylene (PVDF), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), Kynoar-hexafluoropropene (PVDF-HFP) At least one of with aramid fiber.The partial size of the polymer particles be 50~10000nm such as 50nm, 100nm, 500nm, 800nm, 1000nm, 3000nm, 5000nm, 8000nm or 10000nm etc..
Preferably, the mass ratio of the polymer particles and the nano wire is (0.1~5): 1 such as 0.1:1,0.5:1,1: 1,2:1,3:1,4:1 or 5:1 etc.;The quality of the nano wire accounts for the 1~30% of the quality of the solvent such as 1%, 5%, 8%, 10%, 15%, 20%, 25% or 30% etc.;The quality of the adhesive accounts for the 1~50% of the quality of the solvent such as 1%, 5%, 10%, 20%, 30%, 40% or 50% etc..
Preferably, the raw material of the coating fluid further include: auxiliary agent;The quality of the auxiliary agent accounts for the quality of the solvent 0.01~3% such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5% or 3%.
It should be noted that being conducive to improve coating fluid in basement membrane such as polyene after auxiliary agent is added in the raw material of coating fluid The surface tension of hydrocarbon micropore film surface.
Preferably, the adhesive be polyvinyl alcohol, polyacrylonitrile, polyacrylic acid, butadiene-styrene rubber, carboxymethyl cellulose, At least one of Kynoar, polyvinylpyrrolidone and polyimides;The solvent includes water, ethyl alcohol, acetone and N- At least one of methyl pyrrolidone.
Preferably, the auxiliary agent is fluoro-alkyl ethyoxyl alcohol ether, fatty alcohol polyoxyethylene ether, butylbenzene sodium naphthalene sulfonate, hydroxyl At least one of sodium ethylsulfate and lauryl sodium sulfate.
The present invention also provides a kind of preparation method of coating fluid, the coating fluid is above-mentioned coating fluid, the preparation Method includes: to be uniformly mixed each raw material.
Preferably, the preparation method includes: and first disperses nano wire and polymer particles in a solvent, stirring or ultrasound After mixing, adhesive is added, continues stirring or ultrasonic mixing uniformly obtains coating fluid.It further, can also be again Auxiliary agent is continuously added after adhesive is added.
The present invention also provides a kind of lithium ion battery separators, including septum body and are supported in the septum body Coating, the coating are obtained using above-mentioned coating fluid in an at least side surface for the septum body coating, solidification.
Preferably, dip-coating, spraying, spin coating, roller coating or blade coating etc. can be used in the mode of the coating.The cured mode Using hardening with radiation or UV solidification or heat drying solidification in baking oven can be placed in.Preferably, the cured temperature is 40 DEG C~100 DEG C such as 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C, the cured time be 5~120s such as 5s, 10s, 30s, 50s, 80s, 100s or 120s etc..
It should be noted that coating fluid can be for by being coated on the single side surface of septum body (towards certain by above-mentioned coating The one side of one electrode) or septum body double-sided surface (towards two lateral electrodes two sides), then solidification obtain;According to reality Depending on needing.
Preferably, the septum body is microporous polypropylene membrane, polyethene microporous membrane or polypropylene, polyethylene microporous barrier. It should be noted that above-mentioned microporous polypropylene membrane, polyethene microporous membrane or polypropylene, polyethylene microporous barrier are commercial product, Such as it can be made by dry-stretch process.
Preferably, such as 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm or 20 of 3~20 μm of the thickness of the septum body μm etc..
Preferably, the coating with a thickness of 0.01~1 μm as 0.01 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.3 μm, 0.5 μm, 0.8 μm or 1 μm etc..
It should be noted that the nano wire in coating fluid forms the main framing of coating, so that diaphragm has good machinery Intensity, by composition polymer particle, so that diaphragm further has preferable adhesive property.
The present invention will be mixed to get coating fluid using nano wire, polymer particles and adhesive etc. and be coated on septum body Surface, and solidify, it obtains by septum body and the coat composed lithium ion battery separator being supported in the septum body, it should Lithium ion battery separator has good thermal stability and mechanical strength, and has preferable caking property, keeps it viscous with electrode Knot property is good, efficiently solves existing diaphragm there are thermal stability is poor, and its with electrode adhesion difference and lead to the battery of assembling Relatively soft problem;Further, nano wire and polymer particles that the coating material of the lithium ion battery separator uses, can be with Avoid the problem that coating is thicker and the thickness of entire diaphragm and weight is caused to increase, so that it is steady to have reached lithium ion battery separator heat Qualitative good, thickness and weight increase small effect.
The present invention also provides a kind of lithium ion battery of profit, the lithium ion battery include above-mentioned lithium ion battery every Film.
To facilitate the understanding of the present invention, below with reference to embodiment to further illustrate the technical scheme of the present invention.Applicant Statement, the present invention illustrate detailed process equipment and process flow of the invention by following embodiments, but the present invention not office It is limited to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention should rely on following detailed process equipments and technique stream Cheng Caineng is implemented.It should be clear to those skilled in the art, any improvement in the present invention, to each original of product of the present invention The equivalence replacement of material and addition, the selection of concrete mode of auxiliary element etc. all fall within protection scope of the present invention and open model Within enclosing.
Embodiment 1
(1) 27 parts of polymer particles and 30 parts of nano wires is taken to be scattered in 100 parts of ethyl alcohol, after being uniformly mixed, then to 50 parts of butadiene-styrene rubber are added in mixed liquor, continues to be uniformly mixed, obtains coating fluid;Wherein nano wire be diameter be 1~ The carbon nanotube that 100nm and length are 0.1~100 μm, polymer particles are the Kynoar that partial size is 100nm.
(2) coating fluid by step (1) preparation is equably coated on polyethylene micropore film surface by the way of spraying, so Solidify 120s at a temperature of 40 DEG C afterwards;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethene microporous membrane table The coat composed lithium ion battery separator in face, wherein polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 20 μ M, coating with a thickness of 0.05 μm.
Embodiment 2
(1) 7.5 parts of polymer particles and 15 parts of nano wires is taken to be scattered in 100 parts of ethyl alcohol, after being uniformly mixed, then to 25 parts of polyvinyl alcohol are added in mixed liquor, continues to be uniformly mixed, obtains coating fluid;Wherein nano wire be diameter be 1~ The nano-cellulose that 100nm and length are 0.1~100 μm, polymer particles are the polyoxyethylene that partial size is 500nm.
(2) coating fluid by step (1) preparation is equably coated on polyethylene micropore film surface by the way of spraying, so Solidify 50s at a temperature of 70 DEG C afterwards;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethylene micropore film surface Coat composed lithium ion battery separator;Wherein, polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 10 μm, Coating with a thickness of 0.3 μm.
Embodiment 3
(1) 1 part of long nano wire and 10 parts of short nano wires is taken to be scattered in 200 parts of ethyl alcohol, after being uniformly mixed, then to mixed It closes and 15 parts of polyvinyl alcohol is added in liquid, continue to be uniformly mixed, obtain coating fluid;Wherein nano wire be diameter be 1~ The hydroxyapatite nano line that 100nm and length are 0.1~100 μm, polymer particles are the polyoxygenated third that partial size is 1000nm Alkene.
(2) coating fluid by step (1) preparation is equably coated on one surface of polyethene microporous membrane by the way of spraying, Then solidify 5s at a temperature of 100 DEG C;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethene microporous membrane table The coat composed lithium ion battery separator in face;Wherein, polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 5 μ M, coating with a thickness of 1 μm.
Embodiment 4
(1) 2 parts of polymer particles and 10 parts of nano wires are taken to be scattered in 100 parts of ethyl alcohol, after being uniformly mixed, then to mixed It closes and 12 parts of polyvinyl alcohol and 0.1 part of lauryl sodium sulfate is added in liquid, continue to be uniformly mixed, obtain coating fluid;Wherein Wherein nano wire is the carbon nanotube that diameter is 1~100nm and length is 0.1~100 μm, and polymer particles are that partial size is The concave convex rod of 200nm.
(2) coating fluid by step (1) preparation is equably coated on polyethylene micropore film surface by the way of spraying, so Solidify 30s at a temperature of 80 DEG C afterwards;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethylene micropore film surface Coat composed lithium ion battery separator;Wherein, polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 8 μm, Coating with a thickness of 0.5 μm.
Embodiment 5
(1) 6 parts of polymer particles and 10 parts of nano wires are taken to be scattered in 50 parts of ethyl alcohol, after being uniformly mixed, then to mixed It closes and 15 parts of polyvinyl alcohol and 0.5 part of lauryl sodium sulfate is added in liquid, continue to be uniformly mixed, obtain coating fluid;Wherein Wherein nano wire is the carbon nanotube that diameter is 1~100nm and length is 0.1~100 μm, and polymer particles are that partial size is The polyacrylonitrile of 300nm.
(2) coating fluid by step (1) preparation is equably coated on polyethylene micropore film surface by the way of spraying, so Solidify 80s at a temperature of 60 DEG C afterwards;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethylene micropore film surface Coat composed lithium ion battery separator;Wherein, polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 12 μm, Coating with a thickness of 0.1 μm.
Embodiment 6
(1) 8 parts of polymer particles and 10 parts of nano wires is taken to be scattered in 40 parts of molten ethyl alcohol, after being uniformly mixed, then to 16 parts of adhesives and 1.2 parts of lauryl sodium sulfate are added in mixed liquor, continues to be uniformly mixed, obtains coating fluid;Wherein Wherein nano wire is the carbon nanotube that diameter is 1~100nm and length is 0.1~100 μm, and polymer particles are that partial size is The polymethyl methacrylate of 600nm.
(2) coating fluid by step (1) preparation is equably coated on polyethylene micropore film surface by the way of spraying, so Solidify 100s at 50 °C afterwards;It is cooled to room temperature, obtain by polyethene microporous membrane and is carried on polyethene microporous membrane table The coat composed lithium ion battery separator in face;Wherein, polyethene microporous membrane with a thickness of polyethene microporous membrane with a thickness of 18 μ M, coating with a thickness of 0.05 μm.
Embodiment 7
The difference of the embodiment and embodiment 4 is: 4 parts of polymer particles and 10 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
Embodiment 8
The difference of the embodiment and embodiment 4 is: 6 parts of polymer particles and 10 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
Embodiment 9
The difference of the embodiment and embodiment 4 is: 8 parts of polymer particles and 10 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
Embodiment 10
The difference of the embodiment and embodiment 4 is: 3 parts of polymer particles and 15 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
Embodiment 11
The difference of the embodiment and embodiment 4 is: 4 parts of polymer particles and 20 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
Embodiment 12
The difference of the embodiment and embodiment 4 is: 6 parts of polymer particles and 30 parts of nano wires being taken to be scattered in 100 parts of second In alcohol, the other the same as in Example 4.
The thermal stability and peel strength of the lithium ion battery separator of the preparation of above-described embodiment 1~12 are detected, with And lithium ion battery is made using lithium ion battery separator prepared by above-described embodiment 1~12, and examine to its electric property It surveys, testing result is as shown in table 1 below.
Wherein, it diaphragm thermal stability: is measured according to GB/T 21650.1-2008 standard;
Peel strength: it is measured according to GB/T 2792-2014 standard.
Table 1
In table 1, battery main structure having the same in embodiment 1~12, comparative example 1~3, including anode, cathode, Electrolyte and diaphragm, wherein the difference of lithium ion battery separator and embodiment 1~12 in comparative example 1~2 is coating Thickness is thicker;The lithium ion battery separator of comparative example 3 is using polyethene microporous membrane, and the unsupported object for being used to form coating Matter.It should be noted that above-mentioned polyethene microporous membrane is commercial product.
By upper table 1 it is found that using battery diaphragm provided in an embodiment of the present invention, the thermal stability of battery diaphragm and removing Intensity is improved significantly, and at the same time improving the conservation rate of the battery capacity of battery to a certain extent.
It should be added that the septum body in above-described embodiment 1~12 i.e. comparative example 1~3 is replaced with poly- third Alkene microporous barrier or polypropylene, polyethylene microporous barrier can reach above-mentioned identical effect.
The above is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art For member, inventive formulation and preparation process can have various modifications and variations.All within the spirits and principles of the present invention, institute Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of coating fluid for lithium ion battery separator, it is characterised in that: the raw material of the coating fluid include: nano wire, Polymer particles, adhesive and solvent;
The nano wire is nano-cellulose, carbon nanotube, nano-silver thread, boron carbide nano wires, Kocide SD nano wire, aramid fiber At least one of nanofiber, silicon monoxide nano wire and hydroxyapatite nano line;The diameter of the nano wire be 1~ 100nm, length are 0.1~100 μm;
The polymer particles are polyoxyethylene, polypropylene oxide, polyetherimide, Kynoar, polyacrylonitrile, poly- methyl At least one of methyl acrylate, Kynoar hexafluoropropene and aramid fiber, the partial sizes of the polymer particles is 50~ 10000nm。
2. the coating fluid according to claim 1 for lithium ion battery separator, it is characterised in that: the polymer particles Mass ratio with the nano wire is (0.1~5): 1;The quality of the nano wire accounts for the 1~30% of the quality of the solvent;Institute State adhesive quality account for the solvent quality 1~50%.
3. the coating fluid according to claim 1 for lithium ion battery separator, it is characterised in that: the original of the coating fluid Material further include: auxiliary agent;The quality of the auxiliary agent accounts for the 0.01~3% of the quality of the solvent.
4. the coating fluid according to claim 1 for lithium ion battery separator, it is characterised in that: the adhesive is poly- Vinyl alcohol, polyacrylonitrile, polyacrylic acid, butadiene-styrene rubber, carboxymethyl cellulose, Kynoar, polyvinylpyrrolidone and poly- At least one of acid imide;The solvent includes at least one of water, ethyl alcohol, acetone and N-Methyl pyrrolidone.
5. the coating fluid according to claim 3 for lithium ion battery separator, it is characterised in that: the auxiliary agent is fluoro In alkyl ethoxy alcohol ether, fatty alcohol polyoxyethylene ether, butylbenzene sodium naphthalene sulfonate, ethylene hydroxy sulfuric acid sodium and lauryl sodium sulfate It is at least one.
6. a kind of lithium ion battery separator, it is characterised in that: including septum body and the coating that is supported in the septum body, The coating is coated with, admittedly using the described in any item coating fluids of Claims 1 to 5 in an at least side surface for the septum body Change obtains.
7. lithium ion battery separator according to claim 6, it is characterised in that: the mode of the coating be dip-coating, spraying, Spin coating, roller coating or blade coating.
8. lithium ion battery separator according to claim 6, it is characterised in that: the septum body is polypropylene microporous Film, polyethene microporous membrane or polypropylene, polyethylene microporous barrier;3~20 μm of the thickness of the septum body.
9. lithium ion battery separator according to claim 6, it is characterised in that: the coating with a thickness of 0.01~1 μm.
10. a kind of lithium ion battery, it is characterised in that: the lithium ion battery includes the described in any item lithiums of claim 6~9 Ion battery diaphragm.
CN201811014090.4A 2018-08-28 2018-08-31 Coating fluid, lithium ion battery separator and lithium ion battery for lithium ion battery Pending CN109167013A (en)

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CN201811014090.4A CN109167013A (en) 2018-08-31 2018-08-31 Coating fluid, lithium ion battery separator and lithium ion battery for lithium ion battery
US17/255,809 US20210280947A1 (en) 2018-08-28 2019-05-23 Coating Liquid for Use in Lithium Ion Battery, Lithium Ion Battery Separator, and Lithium Ion Battery
JP2020567128A JP7202400B2 (en) 2018-08-28 2019-05-23 Lithium-ion battery coating liquid, lithium-ion battery separator and lithium-ion battery
PCT/CN2019/088088 WO2020042684A1 (en) 2018-08-28 2019-05-23 Coating liquid for use in lithium ion battery, lithium ion battery separator, and lithium ion battery
KR1020207036390A KR102507794B1 (en) 2018-08-28 2019-05-23 Coating liquid used for lithium ion battery, lithium ion battery diaphragm and lithium ion battery
EP19855799.3A EP3846245A4 (en) 2018-08-28 2019-05-23 Coating liquid for use in lithium ion battery, lithium ion battery separator, and lithium ion battery

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534684A (en) * 2019-08-27 2019-12-03 华南理工大学 A kind of polymer-modified diaphragm of one-dimensional nano line and the preparation method and application thereof
CN112909433A (en) * 2021-01-28 2021-06-04 山东大学 Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof
CN113921989A (en) * 2021-09-16 2022-01-11 宁德卓高新材料科技有限公司 Preparation process of flexible diaphragm
WO2022161088A1 (en) * 2021-01-28 2022-08-04 清华大学 Coating material for light-weight lithium ion battery separator, preparation method therefor, and light-weight lithium ion battery composite separator
CN114959765A (en) * 2022-06-01 2022-08-30 润世华新能源控股集团有限公司 Adhesive for membrane electrode, preparation method of membrane electrode slurry, membrane electrode and proton exchange membrane water electrolyzer
WO2023066342A1 (en) * 2021-10-21 2023-04-27 北京宇程科技有限公司 Modified composite separator and preparation method therefor
US11667782B2 (en) 2020-09-09 2023-06-06 Industrial Technology Research Institute Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film
CN114959765B (en) * 2022-06-01 2024-05-03 深圳市润世华氢能源有限公司 Adhesive for membrane electrode, membrane electrode slurry preparation method, membrane electrode and proton exchange membrane water electrolysis tank

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105185940A (en) * 2015-10-23 2015-12-23 旭成(福建)科技股份有限公司 Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm
CN106299222A (en) * 2016-09-05 2017-01-04 东莞新能源科技有限公司 A kind of barrier film and secondary cell thereof
CN107528038A (en) * 2017-08-30 2017-12-29 江苏清陶能源科技有限公司 Prepare the mixed slurry of composite diaphragm and the preparation method of composite diaphragm
CN107565081A (en) * 2017-07-11 2018-01-09 中国科学院上海硅酸盐研究所 A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application
CN107785522A (en) * 2016-08-29 2018-03-09 比亚迪股份有限公司 A kind of lithium ion battery separator and lithium ion battery and preparation method thereof
CN108258171A (en) * 2017-12-29 2018-07-06 深圳中兴创新材料技术有限公司 A kind of high-temperaure coating composite diaphragm and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105185940A (en) * 2015-10-23 2015-12-23 旭成(福建)科技股份有限公司 Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm
CN107785522A (en) * 2016-08-29 2018-03-09 比亚迪股份有限公司 A kind of lithium ion battery separator and lithium ion battery and preparation method thereof
CN106299222A (en) * 2016-09-05 2017-01-04 东莞新能源科技有限公司 A kind of barrier film and secondary cell thereof
CN107565081A (en) * 2017-07-11 2018-01-09 中国科学院上海硅酸盐研究所 A kind of hydroxyapatite overlong nanowire based high-temp-resistant battery diaphragm and its application
CN107528038A (en) * 2017-08-30 2017-12-29 江苏清陶能源科技有限公司 Prepare the mixed slurry of composite diaphragm and the preparation method of composite diaphragm
CN108258171A (en) * 2017-12-29 2018-07-06 深圳中兴创新材料技术有限公司 A kind of high-temperaure coating composite diaphragm and its preparation method and application

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534684A (en) * 2019-08-27 2019-12-03 华南理工大学 A kind of polymer-modified diaphragm of one-dimensional nano line and the preparation method and application thereof
US11667782B2 (en) 2020-09-09 2023-06-06 Industrial Technology Research Institute Polyvinylidene fluoride film composition, and polyvinylidene fluoride isolation film
CN112909433A (en) * 2021-01-28 2021-06-04 山东大学 Silicon monoxide/polyacrylic acid modified high-safety battery diaphragm and preparation method and application thereof
WO2022161088A1 (en) * 2021-01-28 2022-08-04 清华大学 Coating material for light-weight lithium ion battery separator, preparation method therefor, and light-weight lithium ion battery composite separator
CN113921989A (en) * 2021-09-16 2022-01-11 宁德卓高新材料科技有限公司 Preparation process of flexible diaphragm
WO2023066342A1 (en) * 2021-10-21 2023-04-27 北京宇程科技有限公司 Modified composite separator and preparation method therefor
CN114959765A (en) * 2022-06-01 2022-08-30 润世华新能源控股集团有限公司 Adhesive for membrane electrode, preparation method of membrane electrode slurry, membrane electrode and proton exchange membrane water electrolyzer
CN114959765B (en) * 2022-06-01 2024-05-03 深圳市润世华氢能源有限公司 Adhesive for membrane electrode, membrane electrode slurry preparation method, membrane electrode and proton exchange membrane water electrolysis tank

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