CN110444719A - High-strength composite lithium ion battery diaphragm - Google Patents
High-strength composite lithium ion battery diaphragm Download PDFInfo
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- CN110444719A CN110444719A CN201910744699.5A CN201910744699A CN110444719A CN 110444719 A CN110444719 A CN 110444719A CN 201910744699 A CN201910744699 A CN 201910744699A CN 110444719 A CN110444719 A CN 110444719A
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- lithium ion
- ion battery
- tio
- strength composite
- diaphragm
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 238000010041 electrostatic spinning Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 18
- 239000012528 membrane Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000001523 electrospinning Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229920006231 aramid fiber Polymers 0.000 description 4
- 239000002121 nanofiber Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000020764 fibrinolysis Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
- D04H3/14—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic yarns or filaments produced by welding
- D04H3/147—Composite yarns or filaments
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a high-strength composite lithium ion battery diaphragm prepared by subjecting TiO to2The particles are subjected to surface modification and then dissolved in polyacrylonitrile solution to ensure that TiO2Successfully grafted on PAN fiber, and then subjected to composite blending to prepare the high-performance lithium ion battery diaphragm. TiO 22Is very stable in a composite diaphragm and an electrolyte system, and can improve the composite diaphragmThe chemical resistance and the electrochemical performance of the membrane, and because of the high specific surface area and the hydrophilicity, the membrane provides a better channel and a transportation carrier for the free shuttle of lithium ions between electrodes, so that the membrane has excellent mechanical properties and thermal stability at high temperature, the aging of the membrane in the reaction process of a battery is reduced, and meanwhile, the thermal shrinkage performance of the membrane is not influenced, thereby ensuring the safe operation performance of the battery. The preparation method is simple and convenient, the raw materials are simple and easy to obtain, the cost is low, and the industrial production is easy to realize.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high-strength composite lithium ion battery separator.
Background technique
Under oil crisis and the pressure of environmental protection, new energy becomes following the main direction of development, and countries in the world are all big
Power develops new energy.In recent years, lithium battery industry is just gradually replaced lead by the support energetically in the fund of countries in the world, lithium battery
The conventional batteries such as battery have extensive application in new-energy automobile, electric consumers (such as mobile phone, computer, intellectual product
Deng) and energy storage field.During 2012 to 2017, new energy policy is issued, and battery industry blowout has been driven to develop,
Domestic power battery enterprise grows rapidly, and 2018, the impetus that new-energy automobile produces sales volume was surging, and 1 ~ September adds up total sales volume
600000, increase by 98.5 % on a year-on-year basis.
The advantages that lithium ion battery also known as secondary cell, because of its energy density height, environmentally protective, the service life is long, easy to carry,
It receives more and more attention.The working mechanism of lithium ion battery is that lithium ion exists in the charge and discharge process of battery through diaphragm
It shuttles between anode, cathode.Diaphragm be interior layer assembly crucial in lithium battery structure one of, its performance directly affects
The performances such as the interfacial structure of battery, internal resistance, decide circulation, capacity and the security performance of battery, the diaphragm pair haveing excellent performance
Improving battery comprehensive performance has important role.The main function of diaphragm in the battery is isolation positive and negative anodes, prevents the two poles of the earth electric
Son conducting and it is short-circuit, while providing the micro channel that ion back and forth migrates between positive and negative anodes.The commercialization lithium electricity of current main-stream
Diaphragm is that the low melting point and surface using polyethylene and polypropylene as the micro-pore septum of representative, but in view of polyolefine material itself can be low
The problems such as, such microporous barrier can not be supplied to the enough safeties of lithium ion battery, in recent years, a lot of and lithium-ion electric have occurred
The relevant on fire, explosion accident of cell system, the safety of lithium battery directly affects its further market development, under exploitation meets
The new types of diaphragm of generation dynamic lithium battery become research hotspot, especially improvement diaphragm heat-resisting quantity and electrolyte compatibility at
It is urgently solved the problems, such as two big urgent needs.
Currently, the preparation method of diaphragm is broadly divided into dry method, wet process and method of electrostatic spinning.Dry process is not necessarily to solvent, right
Environmental-friendly, technique is relatively simple, high production efficiency, but its microcellular structure is related with the orientation of polymer and crystallinity,
Porosity, thickness and aperture of gained diaphragm etc. are difficult to control, moreover, diaphragm is easily broken off along draw direction, can only assemble
The lithium battery of high current density, poor circulation.Wet process, also known as thermally induced phase separation or phase separation method, this method can be in gels
The volatilization that the composition and solvent of solution are controlled in solidification process can preferably control the hole of film to achieve the purpose that pore-creating
Gap rate, to improve the correlated performance of diaphragm, and also it is not tearable；But wet processing device is complicated, high expensive, the production cycle
It is longer.Method of electrostatic spinning is that effect of the spinning solution in high-voltage electrostatic field by electric field force is drawn into fiber filament, and fiber is being connect
It is further stretched refinement, drying before receipts, finally obtains nano fibrous membrane, the diameter of prepared fiber is smaller, up to several hundred
Nanometer, the electro spinning nano fiber with high-specific surface area and porosity, while the method equipment is simple, cost is not high, made fenestra
Gap is interlocked, and film is in tridimensional network, and lyophily is good, can reduce Li dendrite precipitation phenomenon, thus has been obtained in recent years more next
More concerns, but the problems such as electrostatic spinning film dynamic performance is poor is had also discovered in development process.
In order to solve this problem, a large amount of research has also been made in researcher.As patent of invention CN201811224175.5 is public
A kind of novel lithium battery diaphragm is opened, the new types of diaphragm is a kind of electrostatic spinning diaphragm；The electrostatic spinning diaphragm is to polymerize
Object is main material, and surface is coated with inorganic ceramic material.Although this method coated ceramic layer on electrospinning diaphragm, enhance diaphragm
Mechanical property, but the ceramic layer of this densification also greatly reduces the porosity of electrospinning diaphragm, and increases membrane thicknesses, applies
Thickness degree is also difficult to control, this is extremely unfavorable for free shuttling of the lithium ion in diaphragm, so the capacity of final battery and filling
Discharging efficiency is bad；Patent of invention CN201710059627.8 discloses a kind of non-woven fabrics ceramic diaphragm and preparation method thereof and answers
With preparing non-woven fabrics fiber basement membrane particular by method of electrostatic spinning, then using gas ions enhancing technique for atomic layer deposition at it
Surface carries out atomic layer deposition, so that inorganic matter is uniformly coated on the surface of polymer fiber, forming one-dimensional Polymers fiber is
Core, inorganic matter are the core-shell structure of shell, and are applied in secondary cell, and this method passes through the different spray nozzles knots such as core-shell structure
The method of structure promotes diaphragm mechanical property, but the preparation condition of the method is high, easily clogging during spinning, so
Effect is also undesirable；Patent of invention CN201810385938.8, which is disclosed, a kind of can be used for lithium ion with what method of electrostatic spinning was produced
The preparation method of the p-aramid fiber membrane for polymer of battery, by adding cosolvent, by p-aramid fiber polymer or p-aramid fiber
After Fibrinolysis, it is added thereto inorganic nano ceramic particle to obtain mixed liquor.Through mechanical stirring and ultrasonic treatment so that inorganic
Ceramic particle is uniformly dispersed, and obtains dispersion liquid.Electrostatic spinning is carried out using the dispersion liquid, obtains inorganic/organic hybrid films of coming into being,
It is then dried to get to the p-aramid fiber membrane for polymer that can be used for lithium ion battery produced with electrostatic spinning,
But inorganic nano ceramic particle is easy to reunite, uneven in polymer dispersion, easily there is the problems such as stress defect in product；There are also logical
It crosses using the method that engineering material is basis material and promotes mechanical property, but it is very long to make the engineering material synthesized period by oneself, system
Standby condition is harsh, so whole cost is very high, is not suitable for industrial production.
Polyacrylonitrile is the common used material of electrospinning, has excellent spinnability, prepares polyacrylonitrile diaphragm group using electrospinning
Packed battery can possess preferable cyclicity and capacity, and present excellent electrolyte resistance and thermal stability.But virgin pp
The mechanical property of nitrile electrospinning diaphragm is poor, and mechanical property is difficult to be up to state standards, therefore in the height for ensuring electrospinning diaphragm itself
In the case where the excellent properties such as porosity, thermal stability and electrochemistry, make great efforts to promote the mechanical property of electrospinning diaphragm to be current
The emphasis of research.TiO2Inorganic particulate thermal stability is good, hardness is high, partial size is small, reachable nanoscale, and at low cost, is as electricity
Spin one of the ideal material of diaphragm ceramic material.
Summary of the invention
In view of the above shortcomings of the prior art, the purpose of the present invention is to provide a kind of high-strength composite lithium-ion electrics
Pond diaphragm, solving the problems, such as existing diaphragm, there are mechanical property, thermal stability and chemical property are poor.
To achieve the above object, the present invention adopts the following technical scheme: a kind of high-strength composite lithium ion battery separator, is adopted
It is made using the following method:
1) by TiO2It is dissolved in organic solvent and the mixed solution of deionized water with modifying agent, carries out ultrasound, obtain modified TiO2；
2) the modification TiO for obtaining polyacrylonitrile and step 1)2It is dissolved in organic solvent, heating stirring is uniformly mixed, and is obtained dense
Degree be 13wt% electrospun solution, then by the electrospun solution carry out electrostatic spinning, then by obtained composite fibre through drying,
Hot-pressing processing to get arrive the high-strength composite lithium ion battery separator.
Further, the TiO2Mass ratio with modifying agent is 1:1 ~ 2.
Further, the modifying agent is KH560, KH550, KH570 or KH580.
Further, the organic solvent is N-N dimethyl acetamide, N-N dimethylformamide or N methyl pyrrolidone.
Further, the heating temperature is 40 ~ 80 DEG C, and ultrasonic time is 0.5h ~ 10h
Further, TiO in the electrospun solution2Mass fraction be 1 ~ 5%, preferably 3%.
Further, the spinning rate is 0.00008 ~ 0.00016mm/s；The spinning pressure is 10 ~ 28kV.
Further, the drying temperature be 60 ~ 90 DEG C, drying time be 6 ~ for 24 hours.
Further, temperature is 60 ~ 120 DEG C in the hot-pressing processing, and pressure is 5 ~ 20MPa, and the time is 2 ~ 20min.
In this way, to electrospinning diaphragm carry out certain condition heat treatment, do not change electrospinning diaphragm from height hole, compare table greatly
Under conditions of the features such as area and excellent thermal stability and chemical property, the constraint between reinforcing fiber is further increased
The mechanical property of composite diaphragm.
The present invention also provides can a kind of lithium ion battery, using above-mentioned high-strength composite lithium ion battery separator be made.
Compared with prior art, the invention has the following beneficial effects:
1, TiO in composite lithium ion cell diaphragm of the invention2On polyacrylonitrile nanofiber, the two has reached preferable for grafting
Mutually deposit effect, make TiO2It is dispersed in polyacrylonitrile, reunion and sedimentation phenomenon will not occur.TiO2In composite diaphragm and
It is sufficiently stable in electrolyte system, the chemical-resistance and chemical property of composite diaphragm can not only be improved；And Yin Qigao
Specific surface area and lyophily, for lithium ion between the electrodes and free shuttling provides preferable channel and transport agent.This hair
Bright composite diaphragm have corrosion resistance, good lyophily and hold fluidity, uniform porosity and excellent mechanical property and
The performances such as thermal stability at high temperature solve the problems, such as that existing electrospinning diaphragm mechanical property and thermal stability are poor, reduce every
Aging of film during cell reaction, while the thermal contraction performance of diaphragm will not be impacted, so that it is guaranteed that the peace of battery
Full maneuverability.
2, the present invention prepares high-performance polyacrylonitrile nanofiber/TiO using in method of electrostatic spinning2Compound lithium ion every
Film, in TiO2After middle introducing both sexes structure modifier, in the state of ultrasound and heating, water can occur for both sexes structure modifier
Solution, the silanol of formation hydroxyl (water-wet side), and TiO2The included hydroxyl in surface can with the modifying agent of hydrolysis heating condition
Lower generation condensation reaction forms strong chemical bond, the modifying agent such as hydrogen bond and is centered around TiO2Around, it can reduce between particle
Surface can, reduce agglomeration.During supersonic modifying, both sexes structure modifier and TiO2It is anti-that chemistry occurs for-the OH on surface
Ti-O-Si should be generated and be coated on TiO2Surface promotes TiO2Preferably dispersion.As modified TiO2It is introduced in PAN system
Afterwards, TiO2The chemical bond of surface cladding coupling agent molecule, which can be opened, reacts the modified TiO of generation with PAN free radical activity point2/PAN。
Final PAN long-chain free radical is coupled agent sealing end, TiO2Successfully it is grafted on PAN.Compound blended, preparation size is carried out again
It is uniform, the nano ceramics composite fibre of even particle distribution, i.e. high performance lithium ion battery diaphragm.TiO can either be improved2Group
Poly- phenomenon, and increase TiO2And the combination effect of polyacrylonitrile, makes TiO2It is evenly distributed in polyacrylonitrile, can be effectively reduced
Stress collection moderate defect caused by reuniting because of inorganic particulate.Make it have good chemical property, specific surface area, intensity, mould
Amount and good surface size effect etc., to improve the mechanical property of diaphragm, heat resistance and chemical property.
3, high-strength composite lithium ion battery separator of the invention is applied to lithium ion battery, lithium ion can be improved simultaneously
Mechanical property, thermal stability, chemical-resistance and the security performance of battery, and the diaphragm material is nontoxic, will not make to human body
At injury, simply, conveniently, raw material is simple and easy to get for preparation method, at low cost, easy to industrialized production, before having good application
Scape.
Detailed description of the invention
Fig. 1 is the SEM figure of high-strength composite lithium ion battery separator made from embodiment 1 ~ 5；1%wt indicates embodiment 1,
2%wt indicates embodiment 2, and 3%wt indicates embodiment 3, and 4%wt indicates embodiment 4, and 5%wt indicates embodiment 5(similarly hereinafter)；
Fig. 2 is the mechanical property figure of high-strength composite lithium ion battery separator made from embodiment 1 ~ 5；
Fig. 3 is the hot property figure of high-strength composite lithium ion battery separator made from embodiment 1 ~ 5；A, b are heat under different temperatures
Analysis chart, c, d are mass loss figure under different temperatures；
Fig. 4 is the electrochemical window figure of high-strength composite lithium ion battery separator made from embodiment 1 ~ 5；
Fig. 5 is the impedance diagram of high-strength composite lithium ion battery separator made from embodiment 1 ~ 5.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.Not to experiment in following embodiment
What method was illustrated, be routine operation, and agents useful for same is common commercially available.
One, a kind of high-strength composite lithium ion battery separator
Embodiment 1
1) precise 5g TiO2Be placed in a beaker with 5g KH560, add 15g N-N dimethyl acetamide and 20g go from
Then sub- water places the beaker in ultrasonic machine and is heated to 60 DEG C, ultrasonic 300min.After ultrasound, filtering, drying are obtained
Modified TiO2。
2) modified TiO made from 0.78g polyacrylonitrile and 0.06g step 1) is taken2It is added to 5.16g N-N dimethylacetamide
In amine, heating stirring is sufficiently reacted in oil bath pan, obtains the electrospun solution that concentration is 13wt%, wherein TiO2Additive amount be
1wt% is transferred it in syringe, static several hours, to eliminate bubble.
3) electrospun solution made from step 2 is spinned under the speed of 0.00012mm/s, by institute after the completion of preparation
The composite fibre of preparation places dry 12h in 60 DEG C of baking ovens, then by it under conditions of temperature is 80 DEG C and pressure is 20MPa
Hot pressing 5min to get arrive high-strength composite lithium ion battery separator.
Embodiment 2
1) precise 5g TiO2Be placed in a beaker with 5g KH560, add 15g N-N dimethyl acetamide and 20g go from
Then sub- water places the beaker in ultrasonic machine and is heated to 70 DEG C, ultrasonic 300min.After ultrasound, filtering, drying are obtained
Modified TiO2。
2) modified TiO made from 0.78g polyacrylonitrile and 0.12g step 1) is taken2It is added to 5.16g N-N dimethylacetamide
In amine, heating stirring is sufficiently reacted in oil bath pan, obtains the electrospun solution that concentration is 13wt%, wherein TiO2Additive amount be
2wt% is transferred it in syringe, static several hours, to eliminate bubble.
3) electrospun solution made from step 2 is spinned under the speed of 0.00012mm/s, by institute after the completion of preparation
The composite fibre of preparation places dry 12h in 60 DEG C of baking ovens, then by it under conditions of temperature is 80 DEG C and pressure is 20MPa
Hot pressing 5min to get arrive high-strength composite lithium ion battery separator.
Embodiment 3
1) precise 5g TiO2It is placed in a beaker with 5g KH560, adds 15g N-N dimethyl acetamide, 20g deionization
Then water places the beaker in ultrasonic machine and is heated to 60 DEG C, ultrasonic 300min.After ultrasound, filtering, drying are changed
Property TiO2。
2) modified TiO made from 0.78g polyacrylonitrile and 0.18g step 1) is taken2It is added to 5.16g N-N dimethylacetamide
In amine, heating stirring is sufficiently reacted in oil bath pan, obtains the electrospun solution that concentration is 13wt%, wherein TiO2Additive amount be
3wt% is transferred it in syringe, static several hours, to eliminate bubble.
3) electrospun solution made from step 2 is spinned under the speed of 0.00012mm/s, by institute after the completion of preparation
The composite fibre of preparation places dry 12h in 60 DEG C of baking ovens, then by it under conditions of temperature is 80 DEG C and pressure is 20MPa
Hot pressing 5min to get arrive high-strength composite lithium ion battery separator.
Embodiment 4
1) precise 5g TiO2It is placed in a beaker with 5g KH560, adds 15g N-N dimethyl acetamide, 20g deionization
Then water places the beaker in ultrasonic machine and is heated to 80 DEG C, ultrasonic 300min.After ultrasound, filtering, drying are changed
Property TiO2。
2) modified TiO made from 0.78g polyacrylonitrile and 0.24g step 1) is taken2It is added to 5.16g N-N dimethylacetamide
In amine, heating stirring is sufficiently reacted in oil bath pan, obtains the electrospun solution that concentration is 13wt%, wherein TiO2Additive amount be
4wt% is transferred it in syringe, static several hours, to eliminate bubble.
3) electrospun solution made from step 2 is spinned under the speed of 0.00012mm/s, by institute after the completion of preparation
The composite fibre of preparation places dry 12h in 60 DEG C of baking ovens, then by it under conditions of temperature is 80 DEG C and pressure is 20MPa
Hot pressing 5min to get arrive high-strength composite lithium ion battery separator.
Embodiment 5
1) precise 5g TiO2Be placed in a beaker with 5g KH560, add 15g N-N dimethyl acetamide and 20g go from
Then sub- water places the beaker in ultrasonic machine and is heated to 60 DEG C, ultrasonic 300min.After ultrasound, filtering, drying are obtained
Modified TiO2。
2) modified TiO made from 0.78g polyacrylonitrile and 0.3g step 1) is taken2It is added to 5.16g N-N dimethylacetamide
In amine, heating stirring is sufficiently reacted in oil bath pan, obtains the electrospun solution that concentration is 13wt%, wherein TiO2Additive amount be
5wt% is transferred it in syringe, static several hours, to eliminate bubble.
3) electrospun solution made from step 2 is spinned under the speed of 0.00012mm/s, by institute after the completion of preparation
The composite fibre of preparation places dry 12h in 60 DEG C of baking ovens, then by it under conditions of temperature is 80 DEG C and pressure is 20MPa
Hot pressing 5min to get arrive high-strength composite lithium ion battery separator.
Two, performance verification
1, the composite lithium ion cell diaphragm for preparing embodiment 1 ~ 5 carries out SEM test, as a result as shown in Figure 1.
Can intuitively it find out from figure, TiO2Influence of the additive amount to fiber morphology.Wherein, work as TiO2Additive amount is 1wt%
When, because its content is less, so influencing less, apparent agglomeration, and electrospinning processes mistake do not occur to fiber morphology
Journey is also relatively more smooth；Work as TiO2When additive amount is 2wt%, because its content increases, start TiO occur in fiber2Agglomeration, and
Influence to fiber morphology is very big；But with TiO2When additive amount continues to increase to 3wt%, 4wt%, 5wt%, remaining on can be made
Standby nanofiber, illustrates modified TiO2Preferable electrospun solution can be formed with PAN.But from actual technique it has also been found that
Under same concentration, work as TiO2When additive amount continues to increase, preparation efficiency can be reduced, and the diaphragm prepared is brittle, it cannot
Ideal electrospinning diaphragm is prepared, so by factors such as SEM figure and techniques, this experiment can select the TiO less than 5wt%2As
Additive amount.
2, composite lithium ion cell diaphragm prepared by virgin pp nitrile and embodiment 1 ~ 5 is subjected to Mechanics Performance Testing, knot
Fruit is as shown in Figure 2.
It can be seen from the figure that adding TiO in polyacrylonitrile2Afterwards, the mechanical property of composite diaphragm has obtained mentioning greatly very much
It rises, illustrates inorganic ceramic particle TiO2It plays an important role to the mechanical property for promoting composite diaphragm.Wherein work as TiO2Additive amount exists
When 3wt%, the mechanical property of acquisition is best, can reach 30MPa, is 3 times or so of virgin pp nitrile (PAN) diaphragm；The power of diaphragm
After performance reaches 30 MPa, it is that electrode can completely be isolated, is successfully applied to lithium ion battery.Simultaneously in TiO2Additive amount is
When 1wt%, 2wt%, the mechanical property of composite diaphragm also gets a promotion to a certain extent, but is promoted limited；And work as TiO2Addition
When to 4wt%, 5wt%, although the mechanical property of composite diaphragm is bigger than the mechanical property of pure PAN diaphragm, from their extension at breaks
The angle of rate is not ideal electrospinning diaphragm it is found that this kind of diaphragm easily shows brittle.So even if addition TiO2Inorganic particulate
The mechanical property of composite diaphragm can be increased, but be not that additive amount is The more the better.
3, composite lithium ion cell diaphragm prepared by virgin pp nitrile and embodiment 1 ~ 5 is subjected to thermal performance test, as a result
As shown in Figure 3.
(Fig. 3 a, Fig. 3 b) is prepared by the present invention compound, it is apparent that compared with pure PAN diaphragm from thermogram
Diaphragm is in addition TiO2Afterwards, exothermic peak temperature has moved right nearly 20 DEG C, is increased near 330 DEG C by 310 DEG C of script,
And from mass loss figure (Fig. 3 c, Fig. 3 d) as can be seen that compared with pure PAN diaphragm, composite diaphragm prepared by the present invention is adding
Add TiO2Afterwards, mass loss at high temperature also reduces.For theory, remaining diaphragm is more at high temperature, to battery
Security performance is more secure, because diaphragm loss is fewer, preservation is more complete, can more ensure the security isolation of positive and negative anodes, avoids straight
Contact.Obtaining such one of reason is because of TiO2It is a kind of high-temperature stability material, 500 DEG C or less can be with anatase
Stable structure exists；Secondly, being because of TiO2It is successfully grafted in PAN fiber by modification, the two has reached preferable
Mutually deposit effect, be prepared for ideal PAN/ TiO2Composite diaphragm, so the diaphragm is suitably applied lithium ion battery
In.
4, the composite lithium ion cell diaphragm for preparing embodiment 1 ~ 5 carries out electrochemical window test, as a result such as Fig. 4 institute
Show.
It can be seen from the figure that the electrochemical window of commercialization Celgard diaphragm and pure PAN diaphragm is all relatively low, in 3.5V
Left and right；And add inorganic particulate TiO2Afterwards, the electrochemical window of composite diaphragm is greatly improved, in 5.0V or so.Illustrate TiO2
It is sufficiently stable in composite diaphragm and electrolyte system, own characteristic has been played well, helps resistance toization for promoting composite diaphragm
Performance and chemical property are learned, the safety of battery is more advantageous to.
5, the composite lithium ion cell diaphragm for preparing embodiment 1 ~ 5 carries out testing impedance, as a result as shown in Figure 5.
It can be seen from the figure that the impedance of commercialization Celgard diaphragm is maximum, it is unfavorable for the freedom of lithium ion between the electrodes
Deintercalation；And electrospinning diaphragm because of its porosity, high-specific surface area the features such as, very big advantage is presented in ion percent of pass, because
This its impedance is both less than commercial diaphragm, and adds TiO2Composite diaphragm afterwards also possesses lesser impedance value, illustrates to add TiO2
Lithium ion be will not influence in permeability wherein, instead can because of its high-specific surface area and lyophily, be lithium ion electrode it
Between and free shuttling provides preferable channel and transport agent.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (10)
1. a kind of high-strength composite lithium ion battery separator, which is characterized in that be prepared by the following method:
1) by TiO2It is dissolved in organic solvent and the mixed solution of deionized water, heats and ultrasonic, ultrasound with both sexes structure modifier
After, filtration drying obtains modified TiO2；
2) the modification TiO for obtaining polyacrylonitrile and step 1)2It is dissolved in organic solvent, heating stirring is uniformly mixed, and obtains concentration
For the electrospun solution of 13wt%, the electrospun solution is then subjected to electrostatic spinning, then by obtained composite fibre through drying, heat
Pressure handles to arrive the high-strength composite lithium ion battery separator.
2. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the TiO2With both sexes structure
The mass ratio of modifying agent is 1:1 ~ 2.
3. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the both sexes structure modifier
For KH560, KH550, KH570 or KH580.
4. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the organic solvent is N-N
Dimethyl acetamide, N-N dimethylformamide or N methyl pyrrolidone.
5. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the heating temperature be 60 ~
80 DEG C, ultrasonic time is 0.5 ~ 10h.
6. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that TiO in the electrospun solution2
Mass fraction be 1 ~ 5%, preferably 3%.
7. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the spinning rate is
0.00008-0.00016mm/s；The spinning pressure is 10 ~ 28kV.
8. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that the drying temperature be 60 ~
90 DEG C, drying time be 6 ~ for 24 hours.
9. high-strength composite lithium ion battery separator according to claim 1, which is characterized in that temperature in the hot-pressing processing
It is 60 ~ 120 DEG C, pressure is 5 ~ 20MPa, and the time is 2 ~ 20min.
10. a kind of lithium ion battery using any one of the claim 1 ~ 9 high-strength composite lithium ion battery separator.
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| CN114441408A (en) * | 2022-01-24 | 2022-05-06 | 蜂巢能源科技(无锡)有限公司 | Method for monitoring degree of fibrosis in dry film making process, dry film making method, and preparation method and application of dry electrode plate |
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| CN113140871A (en) * | 2021-03-26 | 2021-07-20 | 西安理工大学 | Diaphragm of self-supporting structure for lithium-sulfur battery and preparation method of diaphragm |
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Application publication date: 20191112 |