CN104466062B - A kind of ceramic diaphragm of boracic and preparation method and application - Google Patents
A kind of ceramic diaphragm of boracic and preparation method and application Download PDFInfo
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- CN104466062B CN104466062B CN201410751072.XA CN201410751072A CN104466062B CN 104466062 B CN104466062 B CN 104466062B CN 201410751072 A CN201410751072 A CN 201410751072A CN 104466062 B CN104466062 B CN 104466062B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Ceramic diaphragm of a kind of boracic and preparation method and application, relates to a kind of ceramic diaphragm.The ceramic diaphragm of described boracic, including barrier film base material, is coated with protective layer at barrier film substrate surface, described protective layer be mainly composed of boracic inorganic matter.Preparation method: joined by tetraethyl orthosilicate in absolute ethyl alcohol, adds the mixed liquor of water, ammoniacal liquor, absolute ethyl alcohol and boric acid, obtains the silicon dioxide granule dispersion liquid of boracic after reaction；The silicon dioxide granule dispersion liquid of boracic is centrifuged and dries, it is thus achieved that silicon-dioxide powdery, then silicon-dioxide powdery is calcined, obtain the silicon-dioxide powdery of boracic；The silicon-dioxide powdery of boracic, carboxymethylcellulose calcium and butadiene-styrene rubber are scattered in the mixed solvent of deionized water and absolute ethyl alcohol, and are coated on polyethylene diagrams, the most i.e. obtain the ceramic diaphragm of boracic.The ceramic diaphragm of described boracic can be as diaphragm application in preparing battery.
Description
Technical field
The present invention relates to a kind of ceramic diaphragm, especially relate to ceramic diaphragm of a kind of boracic and preparation method and application.
Background technology
Lithium ion battery is as a kind of energy density height, output voltage height, memory-less effect, cycle performance excellence, environment
Friendly electrochmical power source system, has good economic benefit, social benefit and strategic importance, is widely used in moving
The dynamic every field such as communication, digital product, and very likely become the topmost power-supply system of energy storage and electric automobile field.
In lithium ion battery, barrier film primarily serves and prevents both positive and negative polarity from contacting and allow the effect of ionic conduction, is battery weight
The part wanted.At present, the barrier film used in the lithium ion battery of commercialization mainly has the polyolefin of microcellular structure
Class diaphragm material, such as polyethylene (Polyethylene, PE), the individual layer or many of polypropylene (Polypropylene, PP)
Tunic.Feature due to polymer itself, although polyalkene diaphragm can provide enough mechanical strengths and change at normal temperatures
Learn stability, but the most then show bigger thermal contraction, thus cause both positive and negative polarity contact and gather rapidly big
Calorimetric, although such as first PP/PE composite diaphragm can occur PE fusing to block in polymer at lower temperature (120 DEG C)
Micropore, block ionic conduction and PP and still play the effect of support and prevent the further generation of electrode reaction, but due to PP
Melting temperature also only have 150 DEG C, when temperature rises rapidly, during melting temperature more than PP, barrier film melting can cause big face
Long-pending short circuit also causes thermal runaway, aggravates thermal accumlation, produces inside battery hyperbar, cause cells burst or blast.In battery
Portion's short circuit is the maximum hidden danger of lithium ion battery security.In order to meet the needs of high capacity lithium ion battery development, develop Gao An
Full property barrier film has become the task of top priority of industry.
Electrolyte affinity owing to polyolefin film is hydrophobic material and highly polar is poor, and polyolefin film cannot quickly absorb
Electrolyte and effectively keep electrolyte, this can extreme influence polyolefin film serviceability in lithium ion battery and have
Fixed leakage risk.At present, the preparation method of ceramic diaphragm is mainly ceramic powder (mainly nanometer or the oxygen of sub-micron
Compound powder, such as Al2O3、SiO2、TiO2Deng), binding agent etc. be dispersed in solvent formation slurry, then by the tape casting or dipping
Method forms ceramic coating at polyalkene diaphragm substrate surface and (sees Journal of Power Sources 195 (2010)
6192–6196；Chinese patent CN200580036709.6, CN200780035135.X etc.).Ceramic coating will improve ceramic powder
The affinity of body and barrier film base material, improve barrier film to the absorption of electrolyte and holding capacity, reduce leakage risk, and improve poly-
Alkene film serviceability in lithium ion battery.
Additionally, lithium ion transference number is an important parameter of lithium rechargeable battery.Lithium ion transference number is the highest, lithium
The energy efficiency of ion battery is the highest.When lithium ion transference number is close to or up 1, the energy efficiency of battery is up to the highest.
This is due to inside secondary cell, on the one hand, the migration of anion can cause the consumption of the energy content of battery；On the other hand,
Owing to the migration velocity of anion is faster than lithium ion, electrolytic salt can be caused in charge and discharge process to produce concentration gradient, produce
Raw concentration polarization, thus reduce the energy efficiency of lithium ion battery.Existing electrolyte system, lithium ion transference number is the most inclined
Low (< 0.3), leverage the energy efficiency of battery.
Summary of the invention
It is an object of the invention to provide ceramic diaphragm of a kind of boracic and preparation method thereof.
It is a further object of the present invention to provide the application in preparing battery of the ceramic diaphragm of described boracic.
The ceramic diaphragm of described boracic, including barrier film base material, is coated with protective layer, described protective layer at barrier film substrate surface
Be mainly composed of boracic inorganic matter.
Described inorganic matter is selected from silica, alundum (Al2O3), titanium dioxide, zirconium dioxide, zinc oxide etc.
At least one；The grain diameter of inorganic matter can be 5nm～50 μm, for uniformity and the validity of application of coating, excellent
Select 50nm～10 μm.
The boron of described boracic inorganic matter can derive from boric acid, sodium tetraborate, lithium tetraborate, potassium borohydride, sodium borohydride,
At least one in lithium borohydride, sodium perborate, kodalk etc.；Preferred boric acid.
Described barrier film base material is selected from the TPO apertured polymeric film of commercialization (such as polyethylene or polyacrylic individual layer or many
Layer composite membrane), non-woven fabrics, one in the polymeric material etc. of secondary cell polymer dielectric, described for secondary
The polymeric material of battery polymer electrolyte is selected from polyethylene glycol oxide, polyacrylonitrile, polymethyl methacrylate, gathers partially
One in PVF, Kynoar-hexafluoropropylene copolymer, polyvinyl alcohol, polyimides etc., and include by with upper body
Blended, the copolymerization system that system is derivative, such as acrylonitrile methyl meth acrylat copolymer etc.；
The thickness of described boracic inorganic matter can be 500nm～50 μm, can be coated with at barrier film base material one side, it is also possible at barrier film
Base material double spread.
The binding agent that described protective layer uses can be water-based binder or organic system binding agent；Described water-based binder is selected from:
Sodium carboxymethylcellulose pyce (CMC) and butadiene-styrene rubber (SBR), gelatin and polyvinyl alcohol (PVA), polyacrylate based terpolymers
Latex (LA132, LA133) etc.；Described organic system binding agent is selected from Kynoar, Kynoar-hexafluoropropene, gathers
One in methyl methacrylate etc.；Water-based binder generally uses water and typically adopts as decentralized medium, organic system binding agent
With 1-METHYLPYRROLIDONE, N,N-dimethylformamide as decentralized medium.
The preparation method of the ceramic diaphragm of described boracic, comprises the following steps:
1) tetraethyl orthosilicate is joined in absolute ethyl alcohol, add the mixed liquor of water, ammoniacal liquor, absolute ethyl alcohol and boric acid, instead
The silicon dioxide granule dispersion liquid of boracic is obtained after should；
2) the silicon dioxide granule dispersion liquid of boracic is centrifuged and dries, it is thus achieved that silicon-dioxide powdery, then by silicon-dioxide powdery
Calcining, obtains the silicon-dioxide powdery of boracic；
3) silicon-dioxide powdery of boracic, carboxymethylcellulose calcium (CMC) and butadiene-styrene rubber (SBR) are scattered in from
In the mixed solvent of sub-water and absolute ethyl alcohol, and it is coated on polyethylene diagrams, the most i.e. obtains the ceramic diaphragm of boracic.
In step 1) in, the proportioning of described tetraethyl orthosilicate, absolute ethyl alcohol, water, ammoniacal liquor, absolute ethyl alcohol and boric acid can be 9
ML: 91mL: 49.5mL: 18mL: 32.5mL: 0.6180g, wherein, tetraethyl orthosilicate, absolute ethyl alcohol, water, ammonia
In terms of volume, boric acid is calculated by mass for water, absolute ethyl alcohol；The molar concentration of described ammoniacal liquor can be 14mol/L；Described reaction
Condition can stir reaction 3h with the speed of 200r/min；Silica in the silicon dioxide granule dispersion liquid of gained boracic
The particle diameter of particle can be 500nm.
In step 2) in, the condition of described calcining can be with 500 DEG C of calcining 6h in Muffle furnace.
In step 3) in, the silicon-dioxide powdery of described boracic, carboxymethylcellulose calcium, butadiene-styrene rubber, deionized water,
The proportioning of absolute ethyl alcohol can be 1.9g: 1.9g: 0.12g: 10mL: 10mL, wherein, the silicon-dioxide powdery of boracic,
Carboxymethylcellulose calcium, butadiene-styrene rubber are calculated by mass, and deionized water, absolute ethyl alcohol are in terms of volume；Described carboxymethyl is fine
The carboxymethylcellulose calcium that dimension element can use mass fraction to be 2%；The fourth that described butadiene-styrene rubber can use mass fraction to be 50%
Benzene rubber；Described coating can use on small size coating machine and be coated on the polyethylene diagrams of 20cm × 6m.
The ceramic diaphragm of described boracic can replace existing ceramic diaphragm as diaphragm application in preparing battery.
Described battery includes the ceramic diaphragm etc. of positive electrode, negative material, boracic, and the ceramic diaphragm of boracic is located at positive pole material
Between material and negative material.
The positive electrode that generally lithium ion battery uses can use in the present invention.The positive active material that positive pole relates to,
The compound of reversibly occlusion-releasing (embedding and deintercalation) lithium ion can be used, use Li for example, it is possible to enumeratexMO2Or
LiyM2O4Lithium-contained composite oxide that (in formula, M is transition metal, 0≤x≤1,0≤y≤2) represents, the oxidation of spinelle shape
Thing, the metal chalcogenide of layer structure, olivine structural etc..
As its object lesson, LiCoO can be enumerated2Deng lithium and cobalt oxides, LiMn2O4Deng lithium manganese oxide, LiNiO2Deng lithium
Nickel oxide, Li4/3Ti5/3O4Deng Li-Ti oxide, li-mn-ni compound oxide, lithium manganese nickel cobalt composite oxides；There is LiMPO4(M
=Fe, Mn, Ni) etc. the material of olivine-type crystalline texture etc..
Lithium-contained composite oxide especially with layer structure or spinelle shape structure is preferred, LiCoO2、LiMn2O4、
LiNiO2、LiNi1/2Mn1/2O2Deng for the li-mn-ni compound oxide of representative, LiNil/3Mn1/3Co1/3O2、LiNi0.6Mn0.2Co0.2O2Deng
For the lithium manganese nickel cobalt composite oxides represented or LiNi1-x-y-zCoxAlyMgzO2(in formula, 0≤x≤1,0≤y≤0.1,0≤z
≤ 0.1,0≤1-x-y-z≤1) etc. lithium-contained composite oxide.It addition, constitution element in above-mentioned lithium-contained composite oxide
A part, lithium-contained composite oxide replaced by the addition element of Ge, Ti, Zr, Mg, Al, Mo, Sn etc. etc. is also
Comprise wherein.
These positive active materials, both can be used alone a kind, it is possible to two or more is also used.Such as, by using layer simultaneously
The lithium-contained composite oxide of shape structure and the lithium-contained composite oxide of spinel structure, can seek to take into account high capacity and safety
The raising of property.
For constituting the positive pole of nonaqueous electrolytic solution secondary battery, such as, be properly added in above-mentioned positive active material carbon black,
The conductive auxiliary agents such as acetylene black, or the adhesive such as Kynoar, PEO etc., prepare anode mixture, by it with aluminium
The current-collecting members such as paper tinsel use as after coating on the banding formed body of core.But, on the preparation method of positive pole is not limited only to
Example.
The negative material that generally lithium ion battery uses can use in the present invention.The negative electrode active material that negative pole relates to can
-removal lithium embedded metal, the compound of lithium can be embedded to use.The alloy of such as aluminium, silicon, tin etc. or oxide, material with carbon element etc.
Various materials etc. can serve as negative electrode active material.Oxide can enumerate titanium dioxide etc., material with carbon element can enumerate graphite,
Pyrolysis carbons, coke class, glassy carbons, the sintered body of organic high molecular compound, mesophase-carbon micro-beads etc..
For constituting the negative pole of nonaqueous electrolytic solution secondary battery, such as, be properly added in above-mentioned negative electrode active material carbon black,
The conductive auxiliary agents such as acetylene black, or the adhesive such as Kynoar, PEO etc., prepare cathode agent, by it with copper
The current-collecting members such as paper tinsel use as after coating on the banding formed body of core.But, on the preparation method of negative pole is not limited only to
Example.
In the nonaqueous electrolytic solution secondary battery that the present invention provides, use nonaqueous solvents (organic solvent) as nonaqueous electrolytic solution.
Nonaqueous solvents includes carbonates, ethers etc..
Carbonates includes cyclic carbonate and linear carbonate, and cyclic carbonate can enumerate ethylene carbonate, propylene carbonate
Ester, butylene, gamma-butyrolacton, sulphur class ester (ethylene glycol sulfide etc.) etc..Linear carbonate can enumerate carbonic acid two
Low viscous polarity linear carbonate that methyl esters, diethyl carbonate, methyl ethyl carbonate etc. are representative, aliphatic branched chain type carbonic acid
Ester type compound.Cyclic carbonate (particularly ethylene carbonate) is particularly preferred with the mixed solvent of linear carbonate.
Ethers can enumerate dimethyl ether tetraethylene glycol (TEGDME), glycol dimethyl ether (DME), 1,3-dioxolane (DOL)
Deng.
It addition, in addition to above-mentioned nonaqueous solvents, the chain phosphorus such as chain-like alkyl esters, trimethyl phosphate such as methyl propionate can be used
Acid three esters；The nitrile solvents such as 3-methoxypropionitrile；The branched chain type compound etc. with ehter bond with dendrimer as representative
Nonaqueous solvents (organic solvent).
It addition, may be used without fluorine kind solvent.
As fluorine kind solvent, for example, it is possible to enumerate H (CF2)2OCH3、C4F9OCH3、H(CF2)2OCH2CH3、H(CF2)2OCH2CF3、
H(CF2)2CH2O(CF2)2H etc. or CF3CHFCF2OCH3、CF3CHFCF2OCH2CH3(perfluoroalkyl) alkyl etc. linear chain structure
Ether, i.e. 2-trifluoromethyl hexafluoro propyl methyl ether, 2-trifluoromethyl hexafluoro propyl group ether, 2-trifluoromethyl hexafluoro propyl group propyl ether,
3-trifluoromethyl octafluoro butyl methyl ether, 3-trifluoromethyl octafluoro butyl ether, 3-trifluoromethyl octafluoro butyl propyl ether, 4-trifluoro
Methyl ten fluorine amyl group methyl ether, 4-trifluoromethyl ten fluorine amyl group ether, 4-trifluoromethyl ten fluorine amyl group propyl ether, 5-trifluoromethyl ten
Difluoro hexyl methyl ether, 5-trifluoromethyl ten difluoro hexyl ether, 5-trifluoromethyl ten difluoro hexyl propyl ether, 6-trifluoromethyl ten
Tetrafluoro heptyl methyl ether, 6-trifluoromethyl ten tetrafluoro heptyl ether, 6-trifluoromethyl ten tetrafluoro heptyl propyl ether, 7-trifluoromethyl ten
Hexafluoro octyl group methyl ether, 7-trifluoromethyl ten hexafluoro octyl group ether, 7-trifluoromethyl ten hexafluoro octyl group propyl ether etc..
It addition, (perfluoroalkyl) alkyl ether of above-mentioned different (perfluoroalkyl) alkyl ether and above-mentioned linear chain structure also can and be used.
As the electrolytic salt used in nonaqueous electrolytic solution, the preferably perchlorate of lithium, organic boron lithium salts, fluorochemical
The lithium salts such as lithium salts, lithium imide salts.
As the example of such electrolytic salt, for example, it is possible to enumerate LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、
LiCF3SO3、LiCF3CO2、LiC2F4(SO3)2、LiN(C2F5SO2)2、LiC(CF3SO2)3、LiCnF2n+1SO3(n≥2)、LiN(RfOSO2)2
(in formula, Rf is fluoroalkyl) etc..In these lithium salts, fluorine-containing organic lithium salt is particularly preferred.Fluorine-containing organic lithium salt,
Owing to anionic property is big and easily separated one-tenth ion, soluble in nonaqueous electrolytic solution.
Electrolyte lithium salt concentration in nonaqueous electrolytic solution, such as, 0.3mol/L (mol/L) is above preferably, more preferably
More than 0.7mol/L, preferably below 1.7mol/L, more preferably below 1.2mol/L.When the concentration of electrolyte lithium salt is too low,
Ionic conduction is spent little, time too high, worries that failing to dissolve electrolytic salt completely separates out.
It addition, in nonaqueous electrolytic solution, it is also possible to add the various additives of the performance that can improve the battery using it, do not make
It is particularly limited to.
Temperature tolerance and high security that ceramic diaphragm is excellent become one of main selection replacing conventional polyolefins barrier film.
Ceramic diaphragm (Ceramic-coated Separators) is on the surface of existing polyolefin micropore film base material, one side
Or double spread one layer protective layer uniform, that be made up of ceramic microparticle etc., form porous security functions barrier film.?
On the basis of ensureing the original fundamental characteristics of polyolefin micropore barrier diaphragm, give barrier film high heat-resisting function, reduce the heat-shrinkable of barrier film,
Thus more effectively reduce inside lithium ion cell short circuit, prevent the battery thermal runaway caused because of internal short-circuit of battery.
The present invention has the boron of electron deficient effect by introducing in inorganic ceramic powder, is coated on barrier film substrate surface.One side
Face reduces the heat-shrinkable of barrier film with this, improves the heat-resisting function of height of barrier film, improves the affinity of barrier film and electrolyte, from
And improve overall security and the stability in use of ceramic diaphragm；On the other hand, improve lithium ion transference number, with improve lithium from
The energy efficiency of sub-secondary cell.
The invention have benefit that: owing to the electron deficient effect of boron can interact with anion in electrolyte, from
And promote dissociating of lithium salts, fixing anion, improves lithium ion transference number.On the one hand, it is possible to avoid because of lithium ion transference number
The electrolytic salt concentration polarization of too low generation, and then the formation of the Li dendrite caused.On the other hand, lithium ion transference number
Raising can effectively promote the energy efficiency of battery.
Accompanying drawing explanation
Fig. 1 be the boracic used by embodiment 1 silica before calcination after and the infrared spectrum of general silica.
Fig. 2 is the stereoscan photograph of the silica of the boracic used by embodiment 1.
The stereoscan photograph of Fig. 3 is embodiment 1 acquisition ceramic diaphragm.
Fig. 4 is embodiment 1, and acquisition ceramic diaphragm compares with the electrolyte wellability of polyethylene diagrams (left: polyethylene every
Film, right: embodiment 1 ceramic diaphragm).
Before Fig. 5 is pyrocondensation test, the obtained ceramic diaphragm of embodiment 1 and polyethylene diagrams (left: polyethylene diagrams, the right side:
Embodiment 1 ceramic diaphragm).
After Fig. 6 is pyrocondensation test, the obtained ceramic diaphragm of embodiment 1 and polyethylene diagrams (left: polyethylene diagrams, the right side:
Embodiment 1 ceramic diaphragm).
Fig. 7 is the embodiment 6 AC impedance spectrogram by steady-state current method test lithium ion transference number.
Fig. 8 is the embodiment 6 steady-state current figure by steady-state current method test lithium ion transference number.
Fig. 9 is the comparative example 2 AC impedance spectrogram by steady-state current method test lithium ion transference number.
Figure 10 is the comparative example 2 steady-state current figure by steady-state current method test lithium ion transference number.
Figure 11 is that embodiment 7 uses the battery of the ceramic diaphragm of the present invention and comparative example 3 to use the electricity of conventional ceramic barrier film
Pond cycle performance correlation curve.
Figure 12 is that embodiment 7 uses the battery of the ceramic diaphragm of the present invention and comparative example 3 to use the electricity of conventional ceramic barrier film
Pond high rate performance correlation curve.
Detailed description of the invention
To be described in more detail by embodiment below, but protection scope of the present invention will be not limited to these enforcement
Example.
Embodiment 1
At normal temperatures 9mL tetraethyl orthosilicate is joined in 91mL absolute ethyl alcohol, be then quickly added into 49.5mL water, 18mL
14mol/L ammoniacal liquor, 32.5mL absolute ethyl alcohol and the mixed liquor of 0.6180g boric acid, stir anti-with the speed of 200r/min
Obtaining the silicon dioxide granule dispersion liquid of boracic after answering 3h, silicon dioxide granule is at about 500nm.By silicon dioxide granule
Dispersion liquid is centrifuged and dries, it is thus achieved that silicon-dioxide powdery.By powder as in Muffle furnace with 500 DEG C of high-temperature calcination 6h, it is thus achieved that
The silicon-dioxide powdery of the boracic after calcining.Take the silicon-dioxide powdery of 1.9g boracic, 1.9g mass fraction is 2%
Carboxymethylcellulose calcium (CMC) and 0.12g butadiene-styrene rubber (SBR) that mass fraction is 50% be scattered in 10mL go from
In the mixed solvent of sub-water and 10mL absolute ethyl alcohol, small size coating machine is carried out on the polyethylene diagrams of 20cm × 6m
Coating, the most i.e. obtains ceramic diaphragm.
Fig. 1 be the boracic used by embodiment 1 silica before calcination after and the infrared spectrum of general silica.Contain
Before calcination, characteristic peak is the silica of boron: 1638cm-1H-OH flexural vibrations；936cm-1Si-OH；1408cm-1
B-O stretching vibration；1108(1120-1020)cm-1Si-O.798,473cm-1Si-O-Si.After calcining,
The peak relevant with-OH disappears (1638cm substantially-1And 936cm-1), new peak: 920cm occurs-1B-O-Si pair
Claim stretching vibration, 676cm-1B-O-Si, can determine whether that boron has been introduced in silica.
Fig. 2 is the stereoscan photograph of the silica of the boracic used by embodiment 1.
Fig. 3 is the stereoscan photograph of the ceramic diaphragm that embodiment 1 obtains.Boracic can be substantially observed from photo
Silicon-dioxide powdery has been laid in the surface of polyethylene diagrams uniformly.
Ceramic diaphragm embodiment 1 obtained and polyethylene diagrams immerse in commercial lithium-ion batteries electrolyte respectively
(the LiPF of 1mol/L6It is dissolved in ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate that mass ratio is 1: 1: 1
In), measure pick up (Electrolyte Uptake) according to the following formula:
Diaphragm quality before pick up=(diaphragm quality before imbibition metacneme quality-imbibition)/imbibition
Embodiment 1 preparation ceramic diaphragm pick up reach 80%, polyethylene diagrams is only 45%, illustrate ceramic diaphragm by
In being coated with ceramic powder, the ability of absorption electrolyte significantly improves.
The ceramic diaphragm preferable electrolyte adsorption capacity that the present invention obtains intuitively can embody from Fig. 4, left side in Fig. 4
Photo after infiltrating in the electrolytic solution for commercially available polyethylene barrier film, right side be the ceramic diaphragm that obtains of the present invention in the electrolytic solution
Photo after infiltration, the electrolyte adsorption capacity of the ceramic diaphragm that the present invention obtains is substantially better than commercially available polyethylene barrier film.
The heat resistanceheat resistant contracting performance of the ceramic diaphragm excellence that the present invention obtains intuitively can embody from Fig. 5 and Fig. 6, left in Fig. 5
Side is the photo of the front commercially available polyethylene barrier film of pyrocondensation experiment, and right side is the ceramic diaphragm photo that the present invention obtains；A left side in Fig. 6
Side is the photo of pyrocondensation experiment (experiment condition is 145 DEG C and keeps 0.5h) commercially available polyethylene barrier film afterwards, and right side is the present invention
The ceramic diaphragm photo obtained；Gather it can be seen that the heat resistanceheat resistant contracting performance of ceramic diaphragm that the present invention obtains is substantially better than commodity
Ethene barrier film.
Comparative example 1
Take 1.9g general silica powder, 1.9g mass fraction be 2% carboxymethylcellulose calcium (CMC) and quality
Mark be 50% 0.12g butadiene-styrene rubber (SBR) be scattered in 10mL deionized water and the mixing of 10mL absolute ethyl alcohol
In solvent, use small size coating machine be coated on the polyethylene diagrams of 20cm × 6m, the most i.e. obtain pottery every
Film.
Embodiment 2
Strong stirring under ice-water bath, instills titanium tetrachloride in distilled water, by the water-soluble drop dissolved with ammonium sulfate and concentrated hydrochloric acid
Being added in the titanium tetrachloride solution of gained, stirring, mixed process temperature controls below 15 DEG C.Add lithium tetraborate, and
After being warming up to 95 DEG C of insulation 1h, adding concentrated ammonia liquor, regulation pH value is about 6.It is cooled to room temperature, is aged 12h, must contain
The TiO 2 particles dispersion liquid of boron, TiO 2 particles is at about 5nm.Titanium dioxide ion dispersion liquid is filtered, washs,
Dry, then be placed in Muffle furnace with 500 DEG C of high-temperature calcination 6h, it is thus achieved that the titanium dioxide powder of the boracic after calcining.Take 4g to contain
The titanium dioxide powder of boron, 1g vinylidene (binding agent) are scattered in 50mlN-methyl pyrrolidone, use curtain coating
Method is at 1m2Polyethylene diagrams on be coated, the most i.e. obtain ceramic diaphragm.
Embodiment 3
Aluminium isopropoxide is dissolved in isopropanol, makes aluminium alcoholates phase；Deionized water, nitric acid, isopropanol are mixed and made into water
Phase.Aluminium alcoholates phase and aqueous phase are simultaneously added dropwise in the reaction vessel filling isopropanol, stirring, make aluminium isopropoxide hydrolyze.
Then add sodium tetraborate.Gel drying is formed hydrated alumina, then calcining obtains the aluminum oxide of boracic at 750 DEG C
Powder, powder is at about 10nm.Take alumina powder jointed, the 2g Kynoar-hexafluoropropene (binding agent) of 8g boracic
It is scattered in 100ml acetone, uses the tape casting at 1m2Polypropylene diaphragm on be coated, the most i.e. obtain pottery
Barrier film.
Embodiment 4
Aqueous zinc acetate solution is added drop-wise in oxalic acid ethanol solution, adds lithium borohydride.Magnetic agitation, it is thus achieved that
Gel.Add, to 70 DEG C, solvent evaporation is obtained xerogel.Grind, by powder as Muffle after being dried 20h in an oven
With 500 DEG C of high-temperature calcination 6h in stove, it is thus achieved that the Zinc oxide powder of the boracic after calcining, powder is at about 300nm.Take this powder
Body 1g, 0.1g Kynoar-hexafluoropropene (binding agent) are scattered in 10ml DMF, use
The mode of immersion coating by its double spread on the polymer film of the Kynoar that thickness is 20 μm, after drying and get final product
To ceramic diaphragm.
Embodiment 5
Being dissolved in absolute ethyl alcohol by zirconium-n-butylate, nitric acid is dissolved in deionized water.By nitric acid and the mixed liquor of deionized water
Dropping in the ethanol solution of alkoxide, magnetic agitation obtains vitreosol, is sealed by colloidal sol, is always changed into solidifying at 40 DEG C of baking ovens
Glue, obtains xerogel under being dried at 40 DEG C after gel adds alcohol ageing, is heat-treated 2h, then as in Muffle furnace with 500 DEG C
High-temperature calcination 6h, it is thus achieved that the Zirconium powder of the boracic after calcining, powder is at about 200nm.Take this powder and gelatin and gather
Vinyl alcohol (PVA) mass ratio 80: 8: 12 mixed powder 1g, puts into deionized water and alcohol mixed solvent 25ml, uses
The mode of immersion coating by its double spread on the polymer film of the Kynoar that thickness is 20 μm, after drying and get final product
To ceramic diaphragm.
Embodiment 6
A kind of simulated battery, including two panels metal lithium sheet, has pottery prepared by embodiment 1 between two panels metal lithium sheet
Barrier film.
Fig. 7 is the embodiment 6 AC impedance spectrogram by steady-state current method test lithium ion transference number.
Fig. 8 is the embodiment 6 steady-state current figure by steady-state current method test lithium ion transference number.
Comparative example 2
A kind of simulated battery, including two panels metal lithium sheet, have prepared by comparative example 1 between two panels metal lithium sheet is common
Ceramic diaphragm.
By steady-state current method testing example 6 and the lithium ion transference number of comparative example 2.Record the lithium ion of embodiment 6
Transport number is 0.91, and the lithium ion transference number of comparative example 2 is 0.23.It can be seen that the lithium ion transference number of the present invention
Lithium ion transference number apparently higher than conventional ceramic barrier film.The raising of lithium ion transference number is it can be avoided that electrolytic salt concentration polarization
Change, prevent the formation of Li dendrite, can effectively promote the energy efficiency of battery simultaneously.
Fig. 9 is the comparative example 2 AC impedance spectrogram by steady-state current method test lithium ion transference number.
Figure 10 is the comparative example 2 steady-state current figure by steady-state current method test lithium ion transference number.
Embodiment 7
A kind of battery, including positive electrode and negative material, has embodiment 1 to make between positive electrode and negative material
Standby ceramic diaphragm.
Comparative example 3
A kind of battery, including positive electrode and negative material, has comparative example 1 to make between positive electrode and negative material
Standby conventional ceramic barrier film.
The cycle performance of battery that testing example 7 obtains with comparative example 3, as shown in figure 11.It can be seen that use this
The cycle performance of battery of the ceramic diaphragm that invention obtains, than the cycle performance of battery of the conventional ceramic barrier film using prior art
It is obviously improved.
The battery high rate performance that testing example 7 and comparative example 3 obtain, as shown in figure 12.It can be seen that experiment is originally
The ceramic diaphragm that invention obtains, owing to introducing the silica of boracic, significantly improves lithium ion transference number, it is achieved lithium ion
Quickly conduction, therefore can improve the battery using this kind of ceramic diaphragm high rate performance under the conditions of high current charge-discharge.
Embodiment 8
A kind of battery, including positive electrode and negative material, has embodiment 2 to prepare between positive electrode and negative material
Ceramic diaphragm.
Embodiment 9
A kind of battery, including positive electrode and negative material, has embodiment 3 to make between positive electrode and negative material
Standby ceramic diaphragm.
Embodiment 10
A kind of battery, including positive electrode and negative material, has embodiment 4 to make between positive electrode and negative material
Standby ceramic diaphragm.
Embodiment 11
A kind of battery, including positive electrode and negative material, has embodiment 5 to make between positive electrode and negative material
Standby ceramic diaphragm.
The electron deficient effect of boron can interact with anion in electrolyte, thus promotes dissociating of lithium salts, fixing cloudy from
Son, improves lithium ion transference number, improves the energy efficiency of the electrochmical power source systems such as lithium ion battery.The pottery that the present invention obtains
Barrier film as the high blowout disk material of the secondary cells such as lithium ion, can have heat endurance and the electrochemistry of excellence
Energy.Strong operability of the present invention, cost is low compared with other method, favorable reproducibility, the constant product quality of gained.
Claims (7)
1. a preparation method for the ceramic diaphragm of boracic, described ceramic diaphragm includes polyethylene diagrams base material, at barrier film base
Material surface is coated with protective layer, described protective layer be mainly composed of boracic silica, it is characterised in that: include following
Step:
1) tetraethyl orthosilicate is joined in absolute ethyl alcohol, adds the mixed liquor of water, ammoniacal liquor, absolute ethyl alcohol and boric acid,
The silicon dioxide granule dispersion liquid of boracic is obtained after reaction；
2) the silicon dioxide granule dispersion liquid of boracic is centrifuged and dries, it is thus achieved that silicon-dioxide powdery, then by silicon dioxide powder
Body is calcined, and obtains the silicon-dioxide powdery of boracic；
3) silicon-dioxide powdery of boracic, carboxymethylcellulose calcium and butadiene-styrene rubber are scattered in deionized water and absolute ethyl alcohol
In mixed solvent, and it is coated on polyethylene diagrams base material, the most i.e. obtains the ceramic diaphragm of described boracic.
2. the preparation method of the ceramic diaphragm of boracic as claimed in claim 1, it is characterised in that described silica
Grain particle diameter is 5nm～50 μm.
3. the preparation method of the ceramic diaphragm of boracic as claimed in claim 2, it is characterised in that described silica
Grain particle diameter is 50nm～10 μm.
4. the preparation method of the ceramic diaphragm of boracic as claimed in claim 1, it is characterised in that described boracic silica
Thickness be 500nm～50 μm.
5. the preparation method of the ceramic diaphragm of boracic as claimed in claim 4, it is characterised in that described boracic silica
One side is coated on barrier film base material, or double spread is on barrier film base material.
6. the preparation method of the ceramic diaphragm of boracic as claimed in claim 1, it is characterised in that in step 1) in, will
9mL tetraethyl orthosilicate joins in 91mL absolute ethyl alcohol, then add 49.5mL enter water, 18mL ammoniacal liquor, 32.5mL without
Water-ethanol and the mixed liquor of 0.6180g boric acid, obtain the silicon dioxide granule dispersion liquid of boracic after reaction；Described ammoniacal liquor
Molar concentration is 14mol/L；Reaction 3h is stirred with the speed of 200r/min；The silicon dioxide granule dispersion of gained boracic
In liquid, the particle diameter of silicon dioxide granule is 500nm；In step 2) in, described calcining refers to forge with 500 DEG C in Muffle furnace
Burn 6h.
7. the preparation method of the ceramic diaphragm of boracic as claimed in claim 1, it is characterised in that in step 3) in, described
The silicon-dioxide powdery of boracic, carboxymethylcellulose calcium, butadiene-styrene rubber, deionized water, the proportioning of absolute ethyl alcohol are 1.9g:
1.9g∶0.12g∶10mL∶10mL；Described carboxymethylcellulose calcium uses mass fraction to be the carboxymethylcellulose calcium of 2%；
Described butadiene-styrene rubber uses mass fraction to be the butadiene-styrene rubber of 50%；Described coating use on small size coating machine 20cm ×
It is coated on the polyethylene diagrams base material of 6m.
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| CN105576178A (en) * | 2016-02-29 | 2016-05-11 | 黄博然 | Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof |
| CN106784558A (en) * | 2017-03-13 | 2017-05-31 | 厦门大学 | Ceramic diaphragm with aeroge as powder and its application in lithium ion battery |
| CN106848396A (en) * | 2017-03-13 | 2017-06-13 | 厦门大学 | A kind of composite polymer electrolyte and preparation method and application |
| CN106848163A (en) * | 2017-03-13 | 2017-06-13 | 厦门大学 | A kind of ceramic coating membrane and its preparation method and application |
| CN110544757A (en) * | 2018-05-29 | 2019-12-06 | 张家港市国泰华荣化工新材料有限公司 | Polymer membrane for sodium-ion battery and preparation method and application thereof |
| CN111097297B (en) * | 2019-12-30 | 2021-10-26 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and application |
| TWI741559B (en) * | 2020-04-13 | 2021-10-01 | 輝能科技股份有限公司 | Composite separating layer |
| CN112795247B (en) * | 2021-01-08 | 2022-05-03 | 厦门大学 | High-viscosity PVDF (polyvinylidene fluoride) coated diaphragm and preparation method thereof |
| CN112928387B (en) * | 2021-01-28 | 2022-05-03 | 厦门大学 | Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm |
| CN115133220A (en) * | 2022-06-27 | 2022-09-30 | 欣旺达电动汽车电池有限公司 | Composite material, preparation method thereof, diaphragm and battery |
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