CN109560238A - Modified diaphragm and preparation method thereof and lithium ion battery - Google Patents
Modified diaphragm and preparation method thereof and lithium ion battery Download PDFInfo
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- CN109560238A CN109560238A CN201811446448.0A CN201811446448A CN109560238A CN 109560238 A CN109560238 A CN 109560238A CN 201811446448 A CN201811446448 A CN 201811446448A CN 109560238 A CN109560238 A CN 109560238A
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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
- H01M50/411—Organic material
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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
- H01M50/403—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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention provides a kind of modified diaphragm and preparation method thereof and lithium ion battery, it includes the polymer that side chain is replaced by sulfonic group lithium in polymer coating that modified diaphragm, which includes barrier film base material and the polymer coating positioned at its surface,.The surface of above-mentioned modified diaphragm interval film base material includes the polymer coating containing sulfonic group lithium group, it has the function of conducting lithium ions, for can be improved the transport number of lithium ion in the electrolytic solution in lithium ion battery, reduce its AC impedance, reduce concentration polarization phenomenon, to slow down or inhibit the growth of battery cathode Li dendrite, the risk of battery short circuit is reduced, effectively improve the security performance of lithium ion battery, high rate performance and extends its service life cycle.The preparation method of modified diaphragm, the polymer-coated that side chain is replaced by sulfonic group lithium is in the surface of barrier film base material, make modified diaphragm also lithium ion transference number with higher when polymer has relatively low degree of substitution, to have the function that slow down lithium dendrite growth.
Description
Technical field
The present invention relates to technical field of lithium ion, in particular to a kind of modified diaphragm and preparation method thereof and lithium ion
Battery.
Background technique
Key component one of of the diaphragm as lithium ion battery, mainly playing prevents positive and negative anodes from contacting and the effect of short circuit,
In addition, the pore structure inside diaphragm constitutes the transmission channel of lithium ion again, the electrochemical reaction of battery is occurred.Every
The structurally and mechanically performance of film will affect charge/discharge capacity, high rate performance, cycle performance and security performance of battery etc..Quotient at present
The lithium ion battery separator of industry is mainly with polypropylene (PP) or polyethylene (PE) for substrate, and in substrate surface coated ceramic
With it is adhesive coated, the wellability of diaphragm can be made to effectively improve, with achieve the purpose that improve battery performance；Diaphragm
Substrate surface coated ceramic and the adhesive coated puncture strength and thermal contraction performance that can also reinforce diaphragm.And it is commercialized electricity
The lithium ion transference number for solving liquid is general relatively low (~0.3), so that battery is easy to produce concentration polarization under the conditions of high current charge-discharge
The phenomenon that change, causes the nonuniform deposition of lithium ion, causes to generate Li dendrite on negative electrode material surface.When lithium dendrite growth to one
Diaphragm may be punctured after determining degree and causes positive and negative anodes short-circuit, thus thermal runaway occurs and the adverse consequences such as even sets off an explosion.
In response to this problem, most of energy storage scholars reduce concentration polarization from the angle of electrolyte, or pass through cathode
Surface modification improves the growth of Li dendrite.Concentration by improving electrolyte will lead to ion to improve the method for concentration polarization
Conductivity reduces；And in the method for negative terminal surface modification, the decorative layer for improving Li dendrite can become in charge and discharge process
It is unstable.Diaphragm is more stable, will not occur above-mentioned problem when inhibiting Li dendrite by modification diaphragm, but not yet
The method that document discloses the angle from modification diaphragm to improve lithium ion transference number, alleviate lithium dendrite growth.
Summary of the invention
The purpose of the present invention is to provide a kind of modified diaphragm and preparation method thereof and lithium ion batteries, to improve diaphragm pair
The conduction of lithium ion, so that the lithium ion transference number for solving lithium ion battery in the prior art is low and is easy to produce battery
The technical issues of concentration polarization generates Li dendrite so as to cause negative terminal surface.
In order to achieve the above objectives, the first aspect of the present invention provides a kind of modified diaphragm, including barrier film base material and is located at
The polymer coating at least one surface of barrier film base material includes what side chain was replaced by sulfonic group lithium in the polymer coating
Polymer.
Further, the degree of substitution of sulfonic group lithium substituent group in the polymer is 20%~100%.
Further, the sulfonic group lithium substituent group is-O-R-SO3Li, wherein R is for the arlydene of C6-C20 or with 1
The inferior heteroaryl of the C3-C9 of~2 nitrogen-atoms optionally the arlydene of the C6-C20 and/or described has 1~2 nitrogen original
The inferior heteroaryl of the C3-C9 of son is further replaced by the alkyl of C1-C6.
Further, R is the arlydene of C6-C14 or five or hexa-atomic inferior heteroaryl with 1 nitrogen-atoms, preferably R choosing
Free phenylene, naphthylene, anthrylene, phenanthrylene, sub-pyridyl group, sub- pyrrole radicals, sub- pyrimidine radicals, sub- quinolyl, sub- isoquinolin
Base and sub- indyl group are in groups.
Further, the presoma of the polymer is selected from by polyphenyl ethers, polyetheretherketone, poly aryl ether ketone and poly-
Sulfone class group is at least one of in groups.
Further, the number-average molecular weight of the polymer is 1,000,000 or more.
It further, further include Kynoar-hexafluoropropylene copolymer in the polymer coating, the polymer applies
Kynoar-hexafluoropropylene copolymer mass percentage described in layer is 20%~50%, the quality of the polymer
Percentage composition is 50%~80%.
Further, the barrier film base material is polypropylene diaphragm, polyethylene diagrams, polyethylene/polypropylene two-layer separator, gathers
Propylene/polyethylene/polypropylene three-layer membrane, nonwoven cloth diaphragm, polyacrylonitrile porous membrane or glass fibre membrane.
Further, the polymer coating with a thickness of 1 μm~5 μm；The barrier film base material with a thickness of 6 μm~15 μ
m。
According to the second aspect of the invention, a kind of preparation method of above-mentioned modified diaphragm is additionally provided, comprising the following steps:
The polymer-coated that side chain is replaced by sulfonic group lithium at least one surface of barrier film base material, can be obtained the modification every
Film.
Further, before the coating step, the preparation method is further comprising the steps of: the polymer is molten
Solution is configured to the solution that the polymer percentage composition is 3wt.%~10wt.% in organic solvent, will optionally gather inclined fluorine
Ethylene-hexafluoropropylene copolymer, which is dissolved in organic solvent, to be configured to the Kynoar-hexafluoropropylene copolymer percentage and contains
Amount is the solution of 0wt.%~50wt.%, and two kinds of solution are uniformly mixed and obtain mixed liquor, and the mixed liquor is coated on diaphragm
At least one surface of substrate.
Further, the number-average molecular weight of the Kynoar-hexafluoropropylene copolymer is 100,000~1,000,000.
Further, the polymer preparation method the following steps are included: (1) with the presoma and bromine of the polymer
The mole ratio for changing reagent 1: 1~4 makes the presoma carry out bromo-reaction, obtains bromo presoma；(2) by the step
(1) presoma of the bromo obtained in replace instead with 3: 1~9 mole ratio with having sulfonic substitution reagent
It answers, presoma after being replaced；(3) presoma after the substitution obtained in the step (2) is added in acid solution
Acidification, is then added lithium hydroxide, and the polymer is obtained after reaction.
Further, the presoma of polymer described in the step (1) be selected from by polyphenyl ethers, polyetheretherketone,
Poly aryl ether ketone and polysulfones group are at least one of in groups；The bromide reagent is that bromine or N- bromo succinyl are sub-
Amine.
Further, the reaction temperature of bromo-reaction described in the step (1) is 100 DEG C~140 DEG C；The bromo is anti-
The degree of bromination answered is 20%~100%.
Further, substitution reagent described in the step (2) is HO-R-SO3M, wherein R be C6-C20 arlydene or
The inferior heteroaryl of C3-C9 with 1~2 nitrogen-atoms optionally the arlydene of the C6-C20 and/or described has 1~2
The inferior heteroaryl of the C3-C9 of a nitrogen-atoms is further replaced by the alkyl of C1-C6；M is metal.
Further, R is the arlydene of C6-C14 or five or hexa-atomic inferior heteroaryl with 1 nitrogen-atoms.
Further, R is selected from by phenylene, naphthylene, anthrylene, phenanthrylene, sub-pyridyl group, sub- pyrrole radicals, sub- pyrimidine
Base, sub- quinolyl, sub- isoquinolyl and sub- indyl group are in groups.
Further, the substitution reagent is selected from -6 sodium sulfonate of beta naphthal, phenylol sodium sulfonate, 4- hydroxyl -3- pyridine -
At least one of sodium sulfonate, hydroxypyrrole sodium sulfonate.
Further, the reaction temperature of substitution reaction described in the step (2) is 50 DEG C~70 DEG C, and the reaction time is
12h~for 24 hours.
Further, the step (3) specifically: presoma after the substitution is dried into film, the film is soaked
It steeps in acid solution, lithium hydroxide is then added, the polymer is obtained after reaction.
Further, the drying temperature of presoma is 50 DEG C~80 DEG C after replacing described in the step (3).
According to the third aspect of the invention we, a kind of lithium ion battery, including the positive electrode, the negative electrode and the separator are additionally provided, it is described
Diaphragm is above-mentioned modified diaphragm or the modified diaphragm that above-mentioned preparation method is prepared.
Modified diaphragm provided by the invention includes the polymer coating of barrier film base material and substrate surface, the polymerization in this coating
Object contains sulfonic group lithium group, has the function of conducting lithium ions, for can be improved lithium ion in lithium ion battery in electricity
The transport number in liquid is solved, its AC impedance is reduced, reduces the concentration polarization phenomenon generated in battery, to slow down or inhibit electricity
The growth of pond cathode Li dendrite, reduces the risk of battery short circuit, effectively improves security performance, the high rate performance of lithium ion battery
And extend its service life cycle.
The preparation method of modified diaphragm provided by the invention, grafts on sulfonic group on the side chain of polymer, then by side
Chain obtains modified diaphragm in the surface of barrier film base material by the polymer-coated that sulfonic group lithium replaces, and modified diaphragm has in polymer
Also lithium ion transference number with higher when relatively low degree of substitution, to have the function that slow down lithium dendrite growth.
Detailed description of the invention
Fig. 1 is the bromo presoma that the preferred embodiment of the present invention 1 and embodiment 2 provide1HNR spectrogram；
Fig. 2 is the cycle performance variation diagram for the lithium ion battery that the preferred embodiment of the present invention 1 and comparative example 1 provide.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below by specific embodiment, the present invention is further described in more detail.
The preferred embodiment of the present invention provides a kind of modified diaphragm, including barrier film base material and is located at barrier film base material surface
Polymer coating, include the polymer that side chain is replaced by sulfonic group lithium in polymer coating.Above-mentioned modified diaphragm is in diaphragm base
The surface of material prepares polymer coating, and the polymer lateral chain in this coating contains sulfonic group lithium group, with conducting lithium ions
Function reduce its AC impedance for can be improved the transport number of lithium ion in the electrolytic solution in lithium ion battery, reduce
The concentration polarization phenomenon generated in battery reduces the wind of battery short circuit to slow down or inhibit the growth of battery cathode Li dendrite
Danger effectively improves the security performance of lithium ion battery, high rate performance and extends its service life cycle.Preferably, diaphragm base
Two surfaces of material are all coated with above-mentioned polymer coating.
In above-mentioned polymer coating, the number-average molecular weight of the polymer containing sulfonic group lithium group is 1,000,000 or more, sulfonic acid
The degree of substitution of base lithium substituent group in the polymer is 20%~100%.The molecular weight of above-mentioned polymer is bigger, and stability is got over
Good, manufactured slurry viscosity is bigger, but when molecular weight is excessive can increase coating difficulty.Substituent group can be grafted in above-mentioned polymer
Active site it is more so that diaphragm coating have higher lithium ion conductivity so that modified diaphragm lithium with higher from
Sub- transport number.However, to will lead to polymer swellbility when excessive larger for the substituent group of grafting, its dimensional stability is made to be deteriorated.
Above-mentioned polymer is in the lower situation of its degree of substitution, same lithium ion conductivity with higher.
Above-mentioned sulfonic group lithium substituent group is-O-R-SO3Li, the arlydene or there is 1~2 nitrogen original that wherein R is C6-C20
The inferior heteroaryl of the C3-C9 of son.Optionally, the sub- heteroaryl of the arlydene of C6-C20 and/or the C3-C9 with 1~2 nitrogen-atoms
Base is further replaced by the alkyl of C1-C6.It is preferred that R is the arlydene of C6-C14 or five or hexa-atomic Asia with 1 nitrogen-atoms
Heteroaryl.More preferable R is selected from by phenylene, naphthylene, anthrylene, phenanthrylene, sub-pyridyl group, sub- pyrrole radicals, sub- pyrimidine radicals, Asia
Quinolyl, sub- isoquinolyl and sub- indyl group are in groups.Above-mentioned sulfonic group lithium substituent group is grafted to polymerization by substitution reaction
On object, the side chain comprising sulfonic group lithium group is formd on polymer, has the function of conducting lithium ions, be used for lithium
It can be improved the transport number of lithium ion in the electrolytic solution in ion battery.
Further, the presoma of polymer is selected from by polyphenyl ethers, polyetheretherketone, poly aryl ether ketone and polysulfones
It organizes at least one of in groups.Contain a large amount of phenyl ring in these polymer, there is preferably stability and mechanical property.
It further include Kynoar-hexafluoropropylene copolymer in above-mentioned polymer coating, Kynoar-hexafluoropropene is total
Mass percentage of the polymers in polymer coating is 20%~50%, the quality for the polymer that side chain is replaced by sulfonic group lithium
Percentage composition is 50%~80%.Kynoar-hexafluoropropylene copolymer plays the role of binder in polymer coating,
Binder content can make the bonding between coating and diaphragm bad when very few.Polymer coating with a thickness of 1 μm~5 μm.On
The thickness for stating polymer coating is too small, does not have the effect of lithium ion conduction；Thickness is too big, influences whether lithium in electrolyte instead
The migration of ion is easy to block diaphragm.
Further, barrier film base material is polypropylene diaphragm, polyethylene diagrams, polyethylene/polypropylene two-layer separator, poly- third
Alkene/polyethylene/polypropylene three-layer membrane, nonwoven cloth diaphragm, polyacrylonitrile porous membrane or glass fibre membrane.The thickness of barrier film base material
It is 6 μm~15 μm.Above-mentioned barrier film base material can prepare the above-mentioned polymer coating containing sulfonic group lithium group on surface and obtain
Modified diaphragm makes modified diaphragm lithium ion transference number with higher.
Embodiment of the present invention also provides a kind of preparation method of above-mentioned modified diaphragm simultaneously, comprising the following steps: will
The polymer-coated that side chain is replaced by sulfonic group lithium is at least one surface of barrier film base material.Preferably, before coating step,
The preparation method of above-mentioned modified diaphragm is further comprising the steps of: will be dissolved in organic solvent and is configured to polymer percentage composition and is
Optional Kynoar-hexafluoropropylene copolymer is dissolved in organic solvent and is configured to by the solution of 3wt.%~10wt.%
Kynoar-hexafluoropropylene copolymer percentage composition is the solution of 0wt.%~50wt.%, and two kinds of solution are uniformly mixed
To mixed liquor, mixed liquor is coated on at least one surface of barrier film base material.Preferably, Kynoar-hexafluoropropene copolymerization
The number-average molecular weight of object is 100,000~1,000,000.The polymer and Kynoar-hexafluoropropene that side chain is replaced by sulfonic group lithium
Copolymer is mixed to form homogeneous phase solution, is homogeneously applied to membrane surface, realizes the modification of diaphragm.60 DEG C~110 after coating
2h~8h is dried under the conditions of DEG C.After two surfaces of diaphragm are coated with, drying obtains modified diaphragm.
In the coating of modified diaphragm, the preparation method for the polymer that side chain is replaced by sulfonic group lithium is the following steps are included: (1)
So that presoma is carried out bromo-reaction with the molar ratio of the presoma of polymer and bromide reagent 1: 1~4, obtains bromo presoma；
(2) bromo presoma obtained in step (1) is replaced with having sulfonic substitution reagent with 3: 1~9 molar ratio
Reaction, presoma after being replaced；(3) presoma, which is added in acid solution, after replacing obtained in step (2) is acidified, so
After lithium hydroxide is added, obtain the polymer that side chain is replaced by sulfonic group lithium after reaction.
In above-mentioned reaction, first with bromide reagent bromine substitution reaction occurs for the presoma of polymer, and difference can be prepared
The bromo presoma of degree of bromination, referring to Fig.1 bromo presoma1HNR spectrogram, from the Bromomethyl Substituted peak product in above-mentioned spectrogram
The long-pending degree of bromination that presoma can be calculated with methyl peak integral area of facet；Then it is added and replaces reagent, Anhydrous potassium carbonate,
Indirect substitution reaction occurs with the brominated polymers in solution, the presoma of sulfonic group substitution is prepared.Above-mentioned polymer
The degree of bromination of presoma is 20%~100%, and degree of substitution is 20%~100%.Herein, degree of bromination indicates polymer molecule
The percentage of hydrogen atom when the bromine atom replaced in chain accounts for unsubstituted refers to the substituted bromine of the hydrogen of methyl on phenyl ring in the present invention
Change degree.Degree of substitution is defined as substitution degree when reagent being replaced to replace different degree of bromination polymer completely.The present invention is implemented
The above-mentioned preparation method that mode provides, enables sulfonic group to graft on the side chain of polymer precursor, and obtained polymer applies
Layer also lithium ion conductivity with higher in relatively low degree of substitution.Next, the presoma that sulfonic group is replaced is molten
Homogeneous phase solution is formed in solvent, is dried into film.Above-mentioned film is impregnated in an acidic solution, preferably soaking time is 12h
~for 24 hours, such as dilute hydrochloric acid, the state that the presoma that sulfonic group replaces is dried into film make it easier for sufficiently connecing with dilute hydrochloric acid
Touching, keeps subsequent reactions more complete, and above-mentioned drying temperature is 50 DEG C~80 DEG C.Addition lithium hydroxide is molten after being washed with water to neutrality
Liquid reaction, obtains the polymer that side chain is replaced by sulfonic group lithium.The polymer that the above-mentioned sulfonic group lithium being prepared is replaced is molten
Kynoar-hexafluoropropylene copolymer is dissolved in organic solvent and is configured to described gather inclined fluorine by the wiring solution-forming in solvent
Ethylene-hexafluoropropylene copolymer percentage composition is the solution of 0wt.%~50wt.%, and two kinds of solution are mixed
Then above-mentioned mixed liquor is formed coating on the surface of diaphragm to get modified diaphragm is arrived by the method for coating by liquid.Above-mentioned modification
Diaphragm lithium ion transference number with higher, can slow down or inhibit the growth of Li dendrite.
In above-mentioned preparation method, it is preferable that the presoma of polymer is selected from by polyphenyl ethers, polyethers ether in step (1)
Ketone, poly aryl ether ketone and polysulfones group are at least one of in groups.Bromide reagent is that bromine or N- bromo succinyl are sub-
Amine.The ratio between mole of presoma and bromide reagent is 1: 1~4.The reaction temperature of presoma and bromide reagent be 100 DEG C~
140℃.Under the above-described reaction conditions, bromo-reaction occurs for presoma and bromide reagent, obtains the polymer of different degree of bromination,
The mole of bromide reagent increases, and the raising of reaction temperature can be such that degree of bromination improves, and degree of bromination is 20%~100%.
Further, it is HO-R-SO that reagent is replaced in step (2)3M, wherein R is for the arlydene of C6-C20 or with 1~2
The inferior heteroaryl of the C3-C9 of a nitrogen-atoms.Optionally, the arlydene of C6-C20 and/or the C3-C9 with 1~2 nitrogen-atoms
Inferior heteroaryl is further replaced by the alkyl of C1-C6.M is metal, such as sodium, potassium, and substitution reagent is sulfonate.Preferably, R is
The arlydene of C6-C14 or five or hexa-atomic sub- heteroaryl with 1 nitrogen-atoms.It is highly preferred that R is selected from by phenylene, sub- naphthalene
Base, anthrylene, phenanthrylene, sub-pyridyl group, sub- pyrrole radicals, sub- pyrimidine radicals, sub- quinolyl, sub- isoquinolyl and sub- indyl institute group
In groups.In the present invention replace reagent be preferably -6 sodium sulfonate of beta naphthal, phenylol sodium sulfonate, 4- hydroxyl -3- pyridine-sodium sulfonate,
At least one of hydroxypyrrole sodium sulfonate.
The ratio between bromo presoma and the mole for replacing reagent, Anhydrous potassium carbonate are 1~3: 1~3: 2~5.In step (2)
Bromo presoma and replace reagent, the reaction temperature of Anhydrous potassium carbonate is 50 DEG C~70 DEG C, the reaction time is 12h~for 24 hours.It is above-mentioned
The hydroxyl that substitution reaction is substituted the bromine in bromo presoma in reagent replaces, and includes sulfonic acid group in obtained polymer.
Wherein, replacing degree of substitution when bromine completely is 20%~100%.
Solvent used in above-mentioned preparation method is selected from by N-Methyl pyrrolidone, N,N-dimethylformamide and two
It is organized in first sulfoxide at least one of in groups.
Embodiment of the present invention also provides a kind of lithium ion battery simultaneously comprising the positive electrode, the negative electrode and the separator, diaphragm are
Above-mentioned modified diaphragm.
Chemical reagent used in the following embodiment is commercially available.
Embodiment 1
Present embodiments provide a kind of modified diaphragm comprising polyethylene diagrams substrate and be located at polyethylene diagrams two
The polyphenylene oxide coating that the side chain on surface is replaced by sulfonic group lithium；Wherein, the porosity of polyethylene diagrams is 40%, with a thickness of 9 μm；
The polyphenylene oxide degree of substitution that side chain is replaced by sulfonic group lithium in polyphenylene oxide coating is 66%, and mass percentage in the coating is
70%, coating with a thickness of 3 μm on each surface of diaphragm.Three groups of parallel tests of above-mentioned modified diaphragm show, lithium ion
Transport number average value is 0.44, and conductivity average value is 0.12mS/cm.
The preparation method of the modified diaphragm of the present embodiment, comprising the following steps:
(1) it weighs polyphenylene oxide to be dissolved in N-Methyl pyrrolidone, is passed through after nitrogen and increases temperature at once to 100 DEG C, to
Wherein the ratio between dropwise addition and polyphenylene oxide mole carry out bromine substitution reaction for 1: 1 bromine.It is molten that solution after reaction is poured into methanol
Product is precipitated in liquid, and is dried after being washed repeatedly with deionized water, obtains bromomethyl polyphenylene oxide.Take bromomethyl obtained above poly-
Phenylate 1mol, -6 sodium sulfonate 1mol of beta naphthal, Anhydrous potassium carbonate 2mol and N-Methyl pyrrolidone 50mL are placed in three-necked flask,
It is passed through nitrogen, magnetic agitation reacts 12h at 50 DEG C, carries out substitution reaction.
(2) solution obtained after reaction is poured slowly into product is precipitated in deionized water, is taken after product is precipitated completely
Out, dry, and be redissolved in N-Methyl pyrrolidone and form homogeneous phase solution, after clock-type funnel filters removal impurity, casting
In horizontal glass culture dish, film, cooling and standings to room temperature are dried at 50 DEG C, and be washed with deionized for several times.It will be thin
Film is soaked in 12h in dilute hydrochloric acid solution, is then washed with deionized to neutrality, and the hydroxide that concentration is 0.5mol/L is added
Lithium solution reaction washs and dry after reaction, obtains sulfonic group lithium polyphenylene oxide.
(3) take above-mentioned sulfonic group lithium polyphenylene oxide be dissolved in be configured in N-Methyl pyrrolidone mass fraction be 3% it is molten
Liquid, taking molecular weight is that 100,000 Kynoar-hexafluoropropylene copolymer is dissolved in N-Methyl pyrrolidone and is configured to quality
The solution that score is 5%, two kinds of solution quality ratios are 1: 1 mixing, stir until dissolved to mixed liquor.
(4) choose porosity be 40%, with a thickness of 9 μm of polyethylene films as barrier film base material, above-mentioned homogeneous phase solution is equal
Even coated on polyethylene film a surface, control coating layer thickness are 3 μm, then dry 5h at 100 DEG C.In above-mentioned polyethylene
Another surface of film repeats operation above, and the thickness of the dosage of mixed liquor and made making coatings is all the same, obtain it is modified every
Film, the i.e. polyethylene diagrams of double measure.
The polyethylene diagrams for the double measure that the present embodiment is prepared are used for CR2430 model button cell, button cell
Lithium piece specification is ф 18*0.5mm, and pole piece diameter is ф 14mm, and voltage window is 0.01V~1.5V, current density 150mA/g
It is tested.For the first time discharge capacity of the above-mentioned battery under 0.1C multiplying power is 133.1mAh/g.Circulating battery uses 100 times, holds
Measuring conservation rate is 97.6%, referring to Fig. 2.
Comparative example 1
The lithium ion battery of this comparative example and the prepared battery difference of the polyethylene diagrams of 1 double measure of embodiment are only
It is the diaphragm using uncoated polyethylene diagrams as lithium ion battery, it is other same as Example 1.Test this comparative example
Battery chemical property, for the first time discharge capacity of the battery under 0.1C multiplying power be 132.7mAh/g.Circulating battery 100 times, hold
Measuring conservation rate is 91.8%, referring to Fig. 2.
Embodiment 2
Present embodiments provide a kind of modified diaphragm comprising polypropylene diaphragm substrate and be located at polypropylene diaphragm two
The poly(aryl ether ketone) coating that the side chain on surface is replaced by sulfonic group lithium；Wherein, the porosity of polypropylene diaphragm is 40%, with a thickness of 9 μ
m；The poly(aryl ether ketone) degree of substitution that side chain is replaced by sulfonic group lithium in poly(aryl ether ketone) coating is 72%, quality percentage in the coating
Content is 70%, coating with a thickness of 3 μm on each surface of diaphragm.Three groups of parallel tests of above-mentioned modified diaphragm show,
Lithium ion transference number average value is 0.55, and conductivity average value is 0.19mS/cm.
The preparation method of the modified diaphragm of the present embodiment, comprising the following steps:
(1) it weighs poly(aryl ether ketone) to be dissolved in N-Methyl pyrrolidone, is passed through after nitrogen and increases temperature at once to 140 DEG C,
The ratio between dropwise addition and poly(aryl ether ketone) mole carry out bromine substitution reaction for 1: 2 bromine thereto.Solution after reaction is poured into first
Product is precipitated in alcoholic solution, and is dried after being washed repeatedly with deionized water, obtains bromomethyl poly(aryl ether ketone).Take bromine obtained above
Methyl poly(aryl ether ketone) 1mol, 4- hydroxyl -3- pyridine-sodium sulfonate 2mol, Anhydrous potassium carbonate 5mol and N-Methyl pyrrolidone 150mL
It is placed in three-necked flask, is passed through nitrogen, magnetic agitation reaction for 24 hours, carries out substitution reaction at 70 DEG C.
(2) solution obtained after reaction is poured slowly into product is precipitated in deionized water, is taken after product is precipitated completely
Out, dry, and be redissolved in N-Methyl pyrrolidone and form homogeneous phase solution, it is cast in after clock-type funnel filters removal impurity
In horizontal glass culture dish, film, cooling and standings to room temperature are dried at 80 DEG C, and be washed with deionized for several times.By film
It is soaked in dilute hydrochloric acid solution for 24 hours, is then washed with deionized to neutrality, and the lithium hydroxide that concentration is 0.5mol/L is added
Solution reaction washs and dry after reaction, obtains sulfonic group lithium poly(aryl ether ketone).
(3) it takes above-mentioned sulfonic group lithium poly(aryl ether ketone) to be dissolved in and is configured to mass fraction in N-Methyl pyrrolidone as 10%
Solution, taking molecular weight is that 1,000,000 Kynoar-hexafluoropropylene copolymer is dissolved in N-Methyl pyrrolidone and is configured to matter
The solution that score is 30% is measured, two kinds of solution quality ratios are 1: 1 mixing, stir until dissolved to mixed liquor.
(4) choose porosity be 40%, with a thickness of 9 μm of polypropylene screens as barrier film base material, above-mentioned homogeneous phase solution is equal
Even coated on polypropylene screen a surface, control coating layer thickness are 3 μm, then dry 5h at 100 DEG C.In above-mentioned polypropylene
Another surface of film repeats operation above, and the thickness of the dosage of mixed liquor and made making coatings is all the same, obtain it is modified every
Film, the i.e. polypropylene diaphragm of double measure.
It is identical as the production of embodiment 1 method of button cell, it makes to obtain electricity by the polypropylene diaphragm of above-mentioned double measure
Pond, testing for the first time discharge capacity of the battery under 0.1C multiplying power is 133.6mAh/g.Circulating battery 100 times, capacity retention ratio
It is 99.1%.
Embodiment 3
Present embodiments provide a kind of modified diaphragm comprising polyethylene/polypropylene two-layer separator substrate and be located at
The polyether-ether-ketone coating that the side chain on two surface of substrate is replaced by sulfonic group lithium；Wherein, the porosity of barrier film base material is 40%, thickness
It is 9 μm；The polyether-ether-ketone degree of substitution that side chain is replaced by sulfonic group lithium in polyether-ether-ketone coating is 78%, quality in the coating
Percentage composition is 70%, coating with a thickness of 3 μm on each surface of diaphragm.Three groups of parallel tests of above-mentioned modified diaphragm are aobvious
Show, lithium ion transference number average value is 0.56, conductivity 0.24mS/cm.
The preparation method of the modified diaphragm of the present embodiment, comprising the following steps:
(1) it weighs polyether-ether-ketone to be dissolved in N-Methyl pyrrolidone, is passed through after nitrogen and increases temperature at once to 140 DEG C,
The ratio between dropwise addition and polyether-ether-ketone mole carry out bromine substitution reaction for 1: 4 bromine thereto.Solution after reaction is poured into first
Product is precipitated in alcoholic solution, and is dried after being washed repeatedly with deionized water, obtains bromomethyl polyether-ether-ketone.Take bromine obtained above
Methyl polyether-ether-ketone 1mol, 4- hydroxyl -3- pyridine-sodium sulfonate 3mol, Anhydrous potassium carbonate 5mol and N-Methyl pyrrolidone 150mL
It is placed in three-necked flask, is passed through nitrogen, magnetic agitation reaction for 24 hours, carries out substitution reaction at 70 DEG C.
(2) solution obtained after reaction is poured slowly into product is precipitated in deionized water, is taken after product is precipitated completely
Out, dry, and be redissolved in N-Methyl pyrrolidone and form homogeneous phase solution, it is cast in after clock-type funnel filters removal impurity
In horizontal glass culture dish, film, cooling and standings to room temperature are dried at 80 DEG C, and be washed with deionized for several times.By film
It is soaked in dilute hydrochloric acid solution for 24 hours, is then washed with deionized to neutrality, and the lithium hydroxide that concentration is 0.5mol/L is added
Solution reaction washs and dry after reaction, obtains sulfonic group lithium polyether-ether-ketone.
(3) it takes above-mentioned sulfonic group lithium polyether-ether-ketone to be dissolved in and is configured to mass fraction in N-Methyl pyrrolidone as 10%
Solution, taking molecular weight is that 500,000 Kynoar-hexafluoropropylene copolymer is dissolved in N-Methyl pyrrolidone and is configured to matter
The solution that score is 50% is measured, two kinds of solution quality ratios are 1: 1 mixing, stir until dissolved to mixed liquor.
(4) choose porosity be 40%, with a thickness of 9 μm of polyethylene/polypropylene two-layer separators as barrier film base material, will be upper
The surface that homogeneous phase solution is evenly applied to substrate is stated, control coating layer thickness is 3 μm, then dries 5h at 100 DEG C.Upper
Another surface for stating substrate repeats operation above, and the thickness of the dosage of mixed liquor and made making coatings is all the same, is changed
Property diaphragm, i.e. the polyethylene/polypropylene diaphragm of double measure.
It is identical as the production of embodiment 1 method of button cell, it is made by the polyethylene/polypropylene diaphragm of above-mentioned double measure
Battery is obtained, testing for the first time discharge capacity of the battery under 0.1C multiplying power is 134.2mAh/g.Circulating battery 100 times, capacity
Conservation rate is 99.6%.
The above description is merely a specific embodiment, but simultaneously difference is limited to this to protection scope of the present invention, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Also, the technical solution between each embodiment of the present invention can be combined with each other, but
To be based on can be realized by those of ordinary skill in the art, when the combination of technical solution occur it is conflicting or can not
Will be understood that the combination of this technical solution is not present when realization, also not the present invention claims protection scope within.Therefore, originally
The protection scope of invention should be based on the protection scope of the described claims.
Claims (20)
1. a kind of modified diaphragm, it is characterised in that: the modified diaphragm includes barrier film base material and is located at the barrier film base material at least
The polymer coating on one surface includes the polymer that side chain is replaced by sulfonic group lithium in the polymer coating.
2. modified diaphragm according to claim 1, which is characterized in that sulfonic group lithium substituent group taking in the polymer
Dai Du is 20%~100%.
3. modified diaphragm according to claim 1, which is characterized in that the sulfonic group lithium substituent group is-O-R-SO3Li,
Middle R is the arlydene of C6-C20 or the inferior heteroaryl of the C3-C9 with 1~2 nitrogen-atoms, optionally, the Asia of the C6-C20
The inferior heteroaryl of aryl and/or the C3-C9 with 1~2 nitrogen-atoms are further replaced by the alkyl of C1-C6.
4. modified diaphragm according to claim 3, which is characterized in that the arlydene or there is 1 nitrogen-atoms that R is C6-C14
Five or hexa-atomic inferior heteroaryl, preferably R is selected from by phenylene, naphthylene, anthrylene, phenanthrylene, sub-pyridyl group, sub- pyrroles
Base, sub- pyrimidine radicals, sub- quinolyl, sub- isoquinolyl and sub- indyl group are in groups.
5. modified diaphragm according to claim 1, which is characterized in that the presoma of the polymer is selected from by polyphenylene oxide
Class, polyetheretherketone, poly aryl ether ketone and polysulfones group are at least one of in groups.
6. modified diaphragm according to claim 1, which is characterized in that the number-average molecular weight of the polymer be 1,000,000 with
On.
7. modified diaphragm according to claim 1, which is characterized in that further include polyvinylidene fluoride in the polymer coating
Alkene-hexafluoropropylene copolymer, Kynoar-hexafluoropropylene copolymer mass percentage described in the polymer coating
It is 20%~50%, the mass percentage of the polymer is 50%~80%.
8. modified diaphragm according to any one of claim 1 to 6, which is characterized in that the thickness of the polymer coating
Be 1 μm~5 μm, the barrier film base material with a thickness of 6 μm~15 μm.
9. a kind of preparation method of modified diaphragm, which comprises the following steps: gathered side chain by what sulfonic group lithium replaced
Close at least one surface that object is coated on barrier film base material.
10. the preparation method of modified diaphragm according to claim 9, which is characterized in that before the coating step, institute
It is further comprising the steps of to state preparation method: the polymer being dissolved in organic solvent and is configured to the polymer percentage composition
For the solution of 3wt.%~10wt.%, optional Kynoar-hexafluoropropylene copolymer is dissolved in organic solvent and is prepared
The solution for being 0wt.%~50wt.% at the Kynoar-hexafluoropropylene copolymer percentage composition mixes two kinds of solution
Mixed liquor uniformly is obtained, the mixed liquor is coated on at least one surface of barrier film base material.
11. the preparation method of modified diaphragm according to claim 10, which is characterized in that the Kynoar-hexafluoro
The number-average molecular weight of propylene copolymer is 100,000~1,000,000.
12. the preparation method of modified diaphragm according to claim 9, which is characterized in that the preparation method of the polymer
The following steps are included:
(1) presoma is made to carry out bromo-reaction with the molar ratio of the presoma of the polymer and bromide reagent 1: 1~4,
Obtain bromo presoma；
(2) the bromo presoma obtained in the step (1) is rubbed with sulfonic substitution reagent with 3: 1~9
You are than carrying out substitution reaction, presoma after being replaced；
(3) presoma after the substitution obtained in the step (2) is added in acid solution and is acidified, hydrogen-oxygen is then added
Change lithium, the polymer is obtained after reaction.
13. the preparation method of modified diaphragm according to claim 12, which is characterized in that gather described in the step (1)
Close object presoma for selected from by polyphenyl ethers, polyetheretherketone, poly aryl ether ketone and polysulfones group in groups at least one
Kind；The bromide reagent is bromine or N- bromo-succinimide.
14. the preparation method of modified diaphragm according to claim 12, which is characterized in that bromine described in the step (1)
The reaction temperature of generation reaction is 100 DEG C~140 DEG C；The degree of bromination of the bromo-reaction is 20%~100%.
15. the preparation method of modified diaphragm according to claim 12, which is characterized in that taken described in the step (2)
It is HO-R-SO for reagent3M, wherein R be C6-C20 arlydene or the C3-C9 with 1~2 nitrogen-atoms inferior heteroaryl, can
The inferior heteroaryl of selection of land, the arlydene of the C6-C20 and/or the C3-C9 with 1~2 nitrogen-atoms are further by C1-
The alkyl of C6 replaces；M is metal.
16. the preparation method of modified diaphragm according to claim 15, which is characterized in that R be C6-C14 arlydene or
Five or hexa-atomic inferior heteroaryl with 1 nitrogen-atoms, preferably R are selected from by phenylene, naphthylene, anthrylene, phenanthrylene, sub- pyrrole
Piperidinyl, sub- pyrrole radicals, sub- pyrimidine radicals, sub- quinolyl, sub- isoquinolyl and sub- indyl group are in groups.
17. the preparation method of modified diaphragm according to claim 12, which is characterized in that taken described in the step (2)
The reaction temperature of generation reaction is 50 DEG C~70 DEG C, and the reaction time is 12h~for 24 hours.
18. the preparation method of modified diaphragm according to claim 12, which is characterized in that the step (3) specifically: will
Presoma is dried into film after the substitution, and the film is soaked in acid solution, lithium hydroxide is then added, after reaction
Obtain the polymer.
19. the preparation method of modified diaphragm according to claim 17, which is characterized in that taken described in the step (3)
Drying temperature for rear presoma is 50 DEG C~80 DEG C.
20. a kind of lithium ion battery, including the positive electrode, the negative electrode and the separator, which is characterized in that the diaphragm is in claim 1~8
The modification that preparation method described in any one of described in any item modified diaphragms or claim 9~19 is prepared every
Film.
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| CN109786637A (en) * | 2019-01-25 | 2019-05-21 | 深圳锂硫科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN111916628A (en) * | 2020-07-14 | 2020-11-10 | 盐山万兴新能源有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN112753112A (en) * | 2020-03-04 | 2021-05-04 | 宁德新能源科技有限公司 | Electrochemical device and electronic device including the same |
| CN113299986A (en) * | 2021-05-24 | 2021-08-24 | 东莞新能安科技有限公司 | Electrolyte membrane, and electrochemical device and electronic device comprising same |
| CN115188962A (en) * | 2022-06-22 | 2022-10-14 | 上海瑞浦青创新能源有限公司 | Lithium ion battery cathode dispersant, preparation method and application |
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| CN103579560A (en) * | 2012-08-01 | 2014-02-12 | 华为技术有限公司 | Battery diaphragm and preparation method thereof, lithium ion battery and communication equipment |
| CN108258307A (en) * | 2016-12-29 | 2018-07-06 | 罗伯特·博世有限公司 | For lithium-battery and/or the protective layer with improved contact of lithium-battery pack |
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| CN103579560A (en) * | 2012-08-01 | 2014-02-12 | 华为技术有限公司 | Battery diaphragm and preparation method thereof, lithium ion battery and communication equipment |
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| CN109786637A (en) * | 2019-01-25 | 2019-05-21 | 深圳锂硫科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN109786637B (en) * | 2019-01-25 | 2019-10-22 | 深圳锂硫科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN112753112A (en) * | 2020-03-04 | 2021-05-04 | 宁德新能源科技有限公司 | Electrochemical device and electronic device including the same |
| US11955661B2 (en) | 2020-03-04 | 2024-04-09 | Ningde Amperex Technology Limited | Electrochemical device and electronic device including the same |
| CN111916628A (en) * | 2020-07-14 | 2020-11-10 | 盐山万兴新能源有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN113299986A (en) * | 2021-05-24 | 2021-08-24 | 东莞新能安科技有限公司 | Electrolyte membrane, and electrochemical device and electronic device comprising same |
| CN115188962A (en) * | 2022-06-22 | 2022-10-14 | 上海瑞浦青创新能源有限公司 | Lithium ion battery cathode dispersant, preparation method and application |
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