CN109980166A - A kind of biomass nano fibre diaphragm, preparation method and application - Google Patents
A kind of biomass nano fibre diaphragm, preparation method and application Download PDFInfo
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- CN109980166A CN109980166A CN201910349678.3A CN201910349678A CN109980166A CN 109980166 A CN109980166 A CN 109980166A CN 201910349678 A CN201910349678 A CN 201910349678A CN 109980166 A CN109980166 A CN 109980166A
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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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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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
- H01M50/44—Fibrous 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
- 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 invention discloses a kind of biomass nano fibre diaphragm, preparation method and application, the biomass nano fibre diaphragm includes the biomass nano fiber film layer with compact texture, has the biomass nano fiber of cyano to be made by chemical modification.In the present invention, due to the modification of cyano, the surface of biomass nano fibre diaphragm can form gel state in conjunction with liquid electrolyte, and lithium ion can be transmitted by the gel state, so that aperture of the transmission of lithium ion independent of diaphragm.Biomass nano fibre diaphragm compactness provided by the invention is good and ionic conductivity is high, electrolyte wellability is good, transference number of ions is high.The invention avoids biomass nano fibre diaphragms to realize high porosity to improve many and diverse step of diaphragm lithium ion conductivity by pore-creating, biomass nano fibre diaphragm provided by the present application has good mechanical performance, realizes the breakthrough that fine and close biomass nano fibre diaphragm equally has excellent electrochemical performance.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of biomass nano fibre diaphragm, preparation method and
Using.
Background technique
Lithium battery includes lithium metal battery, lithium ion battery, and lithium ion battery (LIB) is that comprehensive performance is relatively excellent at present
Power/energy-storage battery.With being continuously increased for high-performance portable electronic product and electric car demand, for lithium-ion electric
Pond energy density, cycle life and the requirement of safety will be substantially improved.Lithium ion battery is mainly by anode, diaphragm, electrolyte
With the several part compositions of cathode；In charge and discharge process, Li+Insertion and deintercalation back and forth between two electrodes.Wherein, as lithium
The key component of ion battery, diaphragm play a part of completely cutting off positive and negative anodes, prevent battery short circuit and conducting lithium ions.According to difference
Physicochemical characteristics, lithium ion battery separator material can be divided into weaving film, microporous barrier, the types such as composite membrane；Good diaphragm is answered
This meets that high mechanical strength, thermostabilization, electrochemically stable, electrolyte wellability be good and the performances such as ionic conductivity height.At present
Commercial battery diaphragm is mainly polyolefin such as polyethylene (PE) and polypropylene (PP), these polyolefin-based separators have goodization
, electrochemical stability and high ionic conductivity.But the mechanical strength of polyalkene diaphragm is weaker, thermal stability is poor,
It may cause positive and negative pole material under high temperature directly to contact, and then make battery short circuit, gather amount of heat so as to cause battery catches fire
Or it explodes.In addition, polyalkene diaphragm is poor to electrolyte wellability, Electolyte-absorptive ability is low, this is easy to lithium-ion electric
The performance in pond generates extreme influence.
Biomass cellulose good, excellent heat stability, not soluble in water and common organic solvents with chemical stability, and
Has the characteristics that good biological degradability.It is existing the study found that having good electricity by diaphragm prepared by biomass nano fiber
Solve that matter wetability, thermal stability be good, the advantages such as at low cost.Also, biomass fiber is renewable resource, and quantity is so huge
Biomass resource provides sufficient substrate source for the development and utilization of biomass fiber.Therefore, biomass nano fiber exists
Application in battery diaphragm has very big prospect.
The method for preparing diaphragm has very much, such as has method of electrostatic spinning to prepare nano fibrous membrane, and vacuum drying film forming
Etc. techniques.However, since biomass nano fiber surface has hydroxyl abundant, during film forming between nanofiber due to
The strong hydrogen bond credit union of hydroxyl generates nonporous film, this causes the ionic conductivity of diaphragm to reduce.In order to improve biomass nano
The ionic conductivity of fibre diaphragm generallys use addition pore creating material or changes the surface in film forming process using organic solvent
The mode of tension, to adjust the aperture of biomass nano fibre diaphragm.But these improved methods are with the shape of diaphragm mesoporous
At will lead to the connection between nanofiber becomes loosely, to reduce the mechanical performance of diaphragm.
Summary of the invention
In view of this, the application's is designed to provide a kind of biomass nano fibre diaphragm, preparation method and application,
Biomass nano fibre diaphragm provided by the present application has good mechanical performance, and ionic conductivity is high.
The present invention provides a kind of biomass nano fibre diaphragms, comprising: the biomass nano fiber with compact texture
Film layer, the biomass nano fiber film layer have the biomass nano fiber of cyano to be made by chemical modification.
Preferably, the biomass nano fibre diaphragm further include: be compounded in the biomass nano fiber film surface
Coat, the coat includes one of ceramic particle and polymer or a variety of.
Preferably, the ceramic particle is selected from one of aluminium oxide, silica and calcium carbonate or a variety of；The polymer
Selected from one of fluoropolymer, poly(aryl ether ketone), polyimides, polymethyl methacrylate and aromatic polysulfonamide or a variety of,
The fluoropolymer is preferably selected from Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylene
Copolymer, vinylidene-trifluoro-ethylene copolymer, fluorinated ethylene propylene copolymer, ethylene tetrafluoroethylene copolymer and ethylene three
One of chlorine fluoride copolymers are a variety of.
Preferably, the biomass nano fiber be selected from one of cellulose nano-fibrous and chitin nanofiber or
It is a variety of；The biomass nano fibre diaphragm with a thickness of 5-500 μm, mechanical tensile strength 10MPa-300MPa.
The present invention also provides a kind of preparation methods of biomass nano fibre diaphragm, comprising the following steps:
S1, biomass nano fiber slurry is provided；
S2, the biomass nano fiber slurry is reacted with dressing agent, the dressing agent is acrylonitrile and different acrylonitrile
One of or it is a variety of, obtain the biomass nano fiber for being modified with cyano；
S3, the biomass nano fiber for being modified with cyano is subjected to copy paper, obtains biomass nano fibre diaphragm.
Preferably, the step S1 specifically:
Biomass nano fiber and dispersion liquid are mixed, is beaten, obtains biomass nano fiber slurry；The biology
Matter nanofiber is selected from one of cellulose nano-fibrous and chitin nanofiber or a variety of；The dispersion liquid be selected from water and
One of ethyl alcohol is a variety of；The mass percent concentration of the biomass nano fiber is 0.01-50%.
Preferably, it in the step S2, is carried out under the conditions of the reaction is existing for the initiator and cosolvent；The initiation
Agent be selected from one of sodium hydroxide, hydrogen peroxide, ammonium ceric nitrate, iron ammonium sulfate, ferric sulfate, potassium peroxydisulfate and ammonium persulfate or
It is a variety of；The cosolvent is selected from one of ethyl alcohol, acetone and acetonitrile or a variety of.
Preferably, in the step S3, the copy paper obtains the biomass nano tunica fibrosa of hygrometric state；
The preparation method further includes step S4: carrying out table on the biomass nano tunica fibrosa of the hygrometric state with coating agent
Face coating, the coating agent include solvent and coating ingredient, described to be applied as point including one of ceramic particle and polymer
Or it is a variety of；Hot pressing and drying are carried out later, obtain biomass nano fibre diaphragm.
Preferably, in the step S4, the solvent is selected from acetone, tetrahydrofuran, n,N-Dimethylformamide and N, N-
One of dimethyl acetamide is a variety of；The biomass nano tunica fibrosa of hygrometric state carries out the pressure of hot pressing after the surface coating
For 0.1MPa-80MPa, temperature is 20 DEG C -100 DEG C.
The present invention also provides biomass nano fibre diaphragms as previously described or previously described preparation method to obtain
Biomass nano fibre diaphragm preparing the application in lithium battery.
Compared with prior art, biomass nano fibre diaphragm provided by the invention includes: the life that surface modification has cyano
Substance nanofiber film layer, with compact texture.In the present invention, due to the modification of cyano, biomass nano fibre diaphragm
Surface gel state can be formed in conjunction with liquid electrolyte, lithium ion can be transmitted by the gel state, so that lithium ion
Transmit the aperture independent of diaphragm.Biomass nano fibre diaphragm compactness provided by the invention is good and ionic conductivity
Height, electrolyte wellability is good, transference number of ions is high.The invention avoids biomass nano fibre diaphragms to be realized by pore-creating
To improve many and diverse step of diaphragm lithium ion conductivity, biomass nano fibre diaphragm provided by the present application has high porosity
Good mechanical performance realizes the breakthrough that fine and close biomass nano fibre diaphragm equally has excellent electrochemical performance.
Detailed description of the invention
Fig. 1 is the infrared test figure of the chitin nanofiber of various concentration of embodiment of the present invention cyano modification；
Fig. 2 is the scanning electron microscope (SEM) photograph of diaphragm prepared by the embodiment of the present invention 1；
Fig. 3 is the tensile strength test of the chitin nano fiber diaphragm of various concentration of embodiment of the present invention cyano modification
Figure；
Fig. 4 is the ionic conductivity test of the chitin nano fiber diaphragm of various concentration of embodiment of the present invention cyano modification
Figure；
Fig. 5 is the scanning electron microscope (SEM) photograph of diaphragm prepared by the embodiment of the present invention 4；
Fig. 6 is the scanning electron microscope (SEM) photograph of diaphragm prepared by the embodiment of the present invention 5；
Fig. 7 is the scanning electron microscope (SEM) photograph of diaphragm prepared by the embodiment of the present invention 6；
Fig. 8 is using diaphragm prepared by the embodiment of the present invention 4 as the long circulating test chart of battery 1 made from battery diaphragm；
Fig. 9 is using diaphragm prepared by the embodiment of the present invention 5 as the long circulating test chart of battery 2 made from battery diaphragm；
Figure 10 is using diaphragm prepared by the embodiment of the present invention 6 as the long circulating test chart of battery 3 made from battery diaphragm；
Figure 11 is using business diaphragm as the long circulating test chart of battery 4 made from battery diaphragm；
Figure 12 is the scanning electron microscope (SEM) photograph of diaphragm prepared by the embodiment of the present invention 8.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of biomass nano fibre diaphragms, comprising: the biomass nano fiber with compact texture
Film layer, the biomass nano fiber film layer have the biomass nano fiber of cyano to be made by chemical modification.
Biomass nano fibre diaphragm provided by the invention has good mechanical performance and higher ionic conductivity, electricity
Chemical property is excellent, conducive to its application in lithium battery.
Biomass nano fibre diaphragm provided by the invention is mainly the biomass nano fiber film layer with compact texture,
It include the compactness film layer of biomass nano fibre composition.Compactness film layer described herein is relative to conventional pore-creating
The porous septum of method preparation and say, it is not without hole, but without using the method for pore-creating so as to cause porosity
Lower (< 15%), aperture are small (< 15nm).
Also, different from conventional common porous separators, herein described biomass nano fiber film layer is had by chemical modification
The biomass nano fiber of cyano is made, and can be described as the biomass nano tunica fibrosa of cyano chemical modification.In the present invention, fiber
Due to the modification of cyano, the surface of biomass nano fibre diaphragm can form gel state in conjunction with liquid electrolyte on surface, lithium from
Son can be transmitted by the gel state, so that aperture of the transmission of lithium ion independent of diaphragm.Therefore, provided by the invention
Biomass nano fibre diaphragm compactness is good, has the characteristics such as good mechanical performance and higher ionic conductivity.
Wherein, the biomass nano fiber is derived from the material of components of biomass, Nano grade fibre morphology, usually
Diameter is less than 100nm, the radial fiber than greater than 100 is defined as nanofiber.Biomass nano fiber is with biomass fiber
Based on element；And chitin is the second largest structural polysaccharide after cellulose, using marine organisms as main source body, such as
Chitin nanofiber is made through chemical treatments such as acid, alkali by shrimp shell.Heretofore described biomass nano fiber can be selected from
One of cellulose nano-fibrous and chitin nanofiber is a variety of, preferably chitin nanofiber；The present invention is to life
The size etc. of substance nanofiber is not specifically limited.
In an embodiment of the present invention, cyano (- CN), cyano are grafted at the biomass nano fiber surface hydroxyl
Degree of substitution can be described as the biomass nano fiber that chemical modification has cyano between 0.01-1.Specifically, degree of substitution=203
(Nb-No)/14(1-Nb+No), NbThe nitrogen content of CCN diaphragm, N are modified for acrylonitrileoIt is the nitrogen content of CCN-0M diaphragm.The present invention
Described in chemical modification there is the biomass nano fiber of cyano to be preferably made according to the following steps:
S1, biomass nano fiber slurry is provided；
S2, the biomass nano fiber slurry is reacted with dressing agent, the dressing agent is acrylonitrile and different acrylonitrile
One of or it is a variety of, obtain the biomass nano fiber for being modified with cyano.
The embodiment of the present invention prepares the slurries containing above-mentioned biomass nano fibrous raw material first, specifically includes: will be biological
Beater is added in matter nanofiber and dispersion liquid according to a certain percentage, is beaten after mixing, and finely dispersed biomass is obtained
Nanofiber slurries.The content of the biomass nano fiber is as previously described；The dispersion liquid is preferably selected from water, and (laboratory is usual
Using deionized water) and one of ethyl alcohol or a variety of.In the biomass nano fiber slurry, the biomass nano
The mass percent concentration of fiber can be 0.01-50%, preferably 0.1-40%, more preferably 0.3-20%.The mashing is
Technological means well-known to those skilled in the art, the present invention are not particularly limited, and divide biomass nano fiber in slurries
It dissipates uniform.
After obtaining biomass nano fiber slurry, the embodiment of the present invention reacts it with dressing agent, and preparation surface chemistry is repaired
The biomass nano fiber of decorations.Specifically, biomass nano fiber slurry, initiator, dressing agent and the cosolvent that can will be obtained
Reaction unit is added by a certain percentage to be reacted；The i.e. described reaction preferably existing for the initiator and cosolvent under the conditions of into
Row.
Wherein, the dressing agent is one of acrylonitrile and different acrylonitrile or a variety of, preferably acrylonitrile.The initiation
Agent is preferably selected from one in sodium hydroxide, hydrogen peroxide, ammonium ceric nitrate, iron ammonium sulfate, ferric sulfate, potassium peroxydisulfate and ammonium persulfate
Kind is a variety of, more preferably sodium hydroxide.The cosolvent is preferably selected from one of ethyl alcohol, acetone and acetonitrile or a variety of, more
Preferably acetone.In the reaction solution of the reaction unit, the mass percent of biomass nano fiber can be 0.01%-
50%；The mass percent of initiator is preferably 0.01%-30%, and the mass percent of dressing agent is preferably 0.01%-90%,
The mass percent of cosolvent is preferably 5%-50%.
In an embodiment of the present invention, the chemical modification reaction refers mainly to biomass fiber surface hydroxyl and unsaturation
The Michael addition reaction of cyano compound；The reaction is general at room temperature, preferably carries out under stirring conditions.Reaction 4
After~6 hours, the embodiment of the present invention can filter reaction mixture, and be cleaned with acetone and water, obtain the life of cyano modification
Substance nanofiber.
Modify cyano after, the biomass nano fiber film layer of compactness is prepared in the embodiment of the present invention, have compared with
High lithium ion conductivity can be applied in the battery of lithium titanate high voltage cathode.
In order to enhance stability of the diaphragm under low potential, biomass nano fibre diaphragm of the present invention is preferably also wrapped
It includes: being compounded in the coat of the biomass nano fiber film surface, the coat includes in ceramic particle and polymer
It is one or more.Biomass nano fiber film surface composite ceramic particle that the embodiment of the present invention is modified in cyano, polymerization
Object coat can be such that diaphragm stablizes under low potential, and can be used in cathode is to open up in lithium metal or this kind of battery of graphite cathode
The wide application range of this kind of diaphragm of the invention.
In coat described in the embodiment of the present invention, the ceramic particle is preferably selected from aluminium oxide, silica and carbonic acid
One of calcium is a variety of, and particle size is preferably 50nm-5 μm.The polymer can be selected from fluoropolymer, poly(aryl ether ketone),
One of polyimides, polymethyl methacrylate and aromatic polysulfonamide are a variety of, and the fluoropolymer is preferably selected from poly-
Vinylidene, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, vinylidene-trifluoro-ethylene
One of copolymer, fluorinated ethylene propylene copolymer, ethylene tetrafluoroethylene copolymer and ethylene trichlorine fluoride copolymers or
It is a variety of；The polymer is preferably one of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer or a variety of；It is described poly-
Closing object number-average molecular weight can be between 50000-1000000.The present invention can coat simultaneously the polymer with ceramic particle；It adopts
With a small amount of polymer, can play the role of adherency ceramic particle prevents it from falling off from diaphragm.
Specifically, the thickness for the biomass nano fibre diaphragm that surface coats in the embodiment of the present invention can be 5 μm -500 μm,
Preferably 10-200 μm, mechanical tensile strength 10MPa-300MPa, preferably greater than 120MPa；Electrolyte absorptivity is 50%-
1000%, dimensional contraction is less than 0.5% at 170 DEG C, and thermal stability is good, electrochemical performance.
The present invention also provides a kind of preparation methods of biomass nano fibre diaphragm, comprising the following steps:
S1, biomass nano fiber slurry is provided；
S2, the biomass nano fiber slurry is reacted with dressing agent, the dressing agent is acrylonitrile and different acrylonitrile
One of or it is a variety of, obtain the biomass nano fiber for being modified with cyano；
S3, the biomass nano fiber for being modified with cyano is subjected to copy paper, obtains biomass nano fibre diaphragm.
Biomass nano fibre diaphragm made from the method for the present invention has good mechanical performance, and ionic conductivity etc.
Electrochemical performance.
The embodiment of the present invention prepares biomass nano fiber slurry first, specifically can be by biomass nano fiber and dispersion liquid
Mixing, is beaten, obtains biomass nano fiber slurry.The biomass nano fiber can be selected from it is cellulose nano-fibrous and
One of chitin nanofiber is a variety of；The dispersion liquid is preferably selected from one of water and ethyl alcohol or a variety of.The present invention
Described in dispersion liquid be preferably deionized water for the selection of water, the pH value of the dispersion liquid is in the range of 1-14.Institute
The preparation process of biomass nano fiber slurry is stated as previously mentioned, this is no longer going to repeat them.
Then, the embodiment of the present invention prepares the biomass nano fiber of surface chemical modification；Obtained biomass can be received
Rice fiber slurry is added reaction unit with raw materials such as dressing agents and is reacted, and obtains chemical modification biomass nano fiber.It is described
Biomass nano fiber slurry includes one of chitin nanofiber slurries, cellulose nanometer slurries or a variety of；It is described anti-
Should preferably existing for the initiator and cosolvent under the conditions of carry out.The type and quality of the initiator, cosolvent and dressing agent
The contents such as concentration are as it was noted above, details are not described herein.
Then, the embodiment of the present invention carries out copy paper to the biomass nano fiber of surface chemical modification；The table that can will be obtained
The biomass nano fiber of face chemical modification on paper machine, carries out copy paper as a slurry.The copy paper is art technology
Technological means known to personnel；It forms a film after copy paper through dehydration, the biomass nano tunica fibrosa of hygrometric state can be obtained.
The present invention it is also preferable to include: carry out surface coating on the biomass nano tunica fibrosa of the hygrometric state with coating agent,
Then hot pressing and drying are carried out, biomass nano fibre diaphragm is obtained.Wherein, the embodiment of the present invention can first be matched using common process
Coating agent processed；The coating agent includes solvent and coating ingredient, described to be applied as point including one in ceramic particle and polymer
Kind is a variety of.
In an embodiment of the present invention, the type of the coating ingredient is as previously described；The solvent can be selected from acetone, tetrahydro
One of furans, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide are a variety of.In coating agent, the coating ingredient
Mass percent concentration be typically not greater than 70%；Wherein mass percent of the polymer in coating agent is 0.1-60%, pottery
The mass percent of porcelain particle is 0.01-70%.The embodiment of the present invention can be by the biology of prepared coating agent dipping to hygrometric state
On matter nano fibrous membrane, the biomass nano fibre diaphragm of surface coating is can be obtained in hot pressing later, drying and winding.It is described
It is preferably 0.1MPa-80MPa, more preferably 0.5- that the biomass nano tunica fibrosa of hygrometric state, which carries out the pressure of hot pressing, after the coating of surface
50MPa, temperature are 20 DEG C -100 DEG C.Specifically, the hot pressing is implemented using the roller press of heating.Dry temperature be 20 DEG C-
200 DEG C, preferably 50-150 DEG C, finally obtain -500 μm of certain thickness diaphragms of dry 5 μm.
After tested, the tensile strength of the obtained diaphragm of the present invention is all larger than 120MPa, and ionic conductivity is higher than polypropylene
Diaphragm.Diaphragm prepared by the present invention in biomass nano fiber surface by being chemically modified, using surface chemical modification
Biomass nano fiber carries out copy paper, is prepared in last handling process by coating processes.The invention avoids biomass
Nanofiber will realize high porosity by pore-creating to improve many and diverse step of ionic conductivity, realize fine and close biomass
Nano fiber diaphragm equally has the breakthrough of excellent electrochemical performance.The present invention greatly optimizes biomass nano fibre diaphragm
Preparation process improves electrolyte wellability, ionic conductivity and transference number of ions etc..
Further, the coating of biomass nano fiber film surface optimizes between biomass nano fibre diaphragm and electrode
Interface stability, improve cycle performance and the lithium battery safety of lithium battery.
The present invention also provides biomass nano fibre diaphragms as previously described, are preparing the application in lithium battery；I.e.
The present invention provides a kind of lithium battery, diaphragm is previously described biomass nano fibre diaphragm.Surface of the present invention
The biomass nano fibre diaphragm of coating can be applied to the fields such as lithium metal battery, lithium-ion-power cell and energy-storage battery, tool
Be widely used range.The present invention is not particularly limited the components such as cathode, electrolyte in lithium battery, and cathode can be lithium
Metal and this kind of traditional material of graphite, or this high voltage cathode of lithium titanate.Lithium battery prepared by the present invention has
Good cycle performance and security performance are conducive to application.
For a further understanding of the application, below with reference to embodiment to a kind of biomass nano fiber provided by the invention every
Film, preparation method and application are specifically described.
In following embodiment, the source of related chitin thin slice is that Weifang Ke Hai chitin Co., Ltd provides, pure
Degree is food-grade.
Embodiment 1
1) the dry chitin thin slice of 3g is dispersed in 1L deionized water, obtains suspension；Acetic acid solution is added later
The pH value of gained suspension is adjusted to 3, is stirred at room temperature 12 hours.The suspension of the chitin thin slice of 0.3wt.% is used
Beater grinds 1h with the speed of 20000r/min, obtains chitin nanofiber slurries.
2) the resulting chitin nanofiber slurries of 1L are poured into 3L beaker, 12g sodium hydroxide is added, stirs evenly
2L acetone is added afterwards, is eventually adding about 180mL acrylonitrile, concentration 1mol/L of the acrylonitrile made in entire mixed solution.
(solvent is acetone, concentration 1M) is stirred at room temperature 5 hours.It filters later, and cleans two with acetone and deionized water respectively
It is secondary, obtain the chitin nanofiber (being denoted as CCN-1M) of 3g cyano modification.
Fig. 1 is the infrared test figure of the chitin nanofiber of various concentration cyano modification, unmodified chitin nanometer
Fiber is denoted as CCN-0M, according to same steps but is added without acrylonitrile solution and is made.By modification front and back infrared spectrum
Comparison, can be clearly apparent the infrared absorption peak of cyano, it was demonstrated that cyano is grafted on fiber really.
The chitin nanofiber that gained cyano is modified is re-dispersed into deionized water, obtaining concentration is 0.3wt.%
Cyano modification chitin nanofiber slurries.
3) the chitin nanofiber slurries that resulting cyano is modified are subjected to copy paper on a papermaking machine, then through being dehydrated into
Film obtains the chitin nano fibrous membrane of the cyano modification of hygrometric state.Later to the chitin nanofiber of the cyano modification of hygrometric state
Film is dried, and dry temperature is 70 DEG C, time 12h, and the chitin nano fiber diaphragm for obtaining cyano modification (is also denoted as
CCN-1M).Its area is 1m2, with a thickness of 20 μm, scanning electron microscope (SEM) photograph is as shown in Figure 2.The cyanogen obtained can be intuitively found out from Fig. 2
Aperture very little, the i.e. resulting biomass nano fibre diaphragm of the present embodiment possessed by the chitin nano fiber diaphragm of base modification
With compact texture.
The chitin nano fiber diaphragm that resulting cyano is modified carries out the performances such as mechanical strength, ionic conductivity and surveys
Examination.Wherein, mechanical strength test is carried out using tester for elongation, tensile speed 0.5mm/min, and the size of each sample is
Width 1cm, length 7cm.Ionic conductivity is obtained by the impedance spectrum of test absorption electrolyte metacneme.
Fig. 3 is the tensile strength test chart of the chitin nano fiber diaphragm of various concentration cyano modification, wherein unmodified
Chitin nano fiber diaphragm be denoted as CCN-0M (being made by unmodified chitin nanofiber according to same steps).From figure
3 can find, the tensile strength of modification front and back chitin nano fiber diaphragm does not change substantially, wherein CCN-0M, CCN-1M,
The tensile strength of CCN-3M, CCN-5M are respectively 142MPa, 133MPa, 128MPa and 122MPa.
Fig. 4 is the ionic conductivity test chart of the chitin nano fiber diaphragm of various concentration cyano modification, wherein is not repaired
The chitin nano fiber diaphragm of decorations is denoted as CCN-0M, and (thickness is about with commercial 2400 lithium ion battery separator of Celgard
25 μm) as a comparison, it is denoted as PP.By the ionic conductivity comparison of modification front and back, it is possible to find the chitin Nanowire after modification
The ionic conductivity for tieing up diaphragm improves a lot (wherein CCN-0M, CCN-1M, CCN- relative to unmodified ionic conductivity
The ionic conductivity of 3M, CCN-5M are respectively 0.035mS/cm, 0.31mS/cm, 0.45mS/cm and 0.37mS/cm), and with
Commercial polypropylene lithium ion battery separator is quite (ionic conductivity of PP diaphragm is 0.45mS/cm).
Embodiment 2~3
It is prepared according to the step 1) in embodiment 1 with step 2), difference is, the acrylonitrile being added in step 2) is dense
Degree is respectively 3M, 5M, and respectively obtaining chitin nanofiber CCN-3M, CCN-5M of cyano modification, (cyano degree of substitution is respectively
0.235,0.234).Infrared spectrum can be clearly apparent the red of cyano by the comparison of modification front and back infrared spectrum referring to Fig. 1
Outer absorption peak, it was demonstrated that cyano is grafted on fiber really.
It is corresponding, according to the step 3) in embodiment 1, the chitin nano fiber diaphragm of cyano modification is prepared respectively
CCN-3M、CCN-5M。
It is tested for the property according to the test method of embodiment 1, tensile property test result is referring to Fig. 3, various concentration third
The tensile strength that alkene nitrile modifies obtained diaphragm is all larger than 120MPa.Ionic conductivity test result referring to fig. 4, various concentration
The ionic conductivity of chitin nano fiber diaphragm after acrylonitrile modification has larger relative to the ionic conductivity that do not modify
It improves, it is suitable with the ionic conductivity that polypropylene diaphragm is tested.
In addition, the present invention, which carries out electrolyte, absorbs test.Specifically, weighing in glove box in diaphragm quality, it is denoted as M1,
Quality is M2 after Electolyte-absorptive.The calculation formula of electrolyte absorptivity are as follows: absorptivity=(M2-M1)/M1 × 100%.As a result
It include: PP film, CCN-0M, CCN-1M, CCN-3M, CCN-5M are respectively 78%, 220%, 320%, 440% and 420%.
Obtained chitin fiber diaphragm electrolyte absorptivity is 50%-1000%, and dimensional contraction is less than at 170 DEG C
0.5%, thermal stability is good, electrochemical performance.
Embodiment 4
By 9g calcium carbonate (granular size be 1 μm), 1g Kynoar-hexafluoropropylene copolymer, (number-average molecular weight is
400000, following embodiment is identical) and 50mL acetone be mixed evenly, obtain coating agent.It is repaired with the resulting cyano of embodiment 2
The chitin nano fibrous membrane of decorations is basement membrane, using dipping method, coats one layer of coating agent in membrane surface.Obtain the carbonic acid of hygrometric state
The chitin nano fibrous membrane of calcium coating and cyano modification.Later by resulting chitin nano fibrous membrane at 70 DEG C, 1MPa into
Row hot pressing, the dry 12h at 70 DEG C, obtains biomass nano fibre diaphragm later.
The average thickness of finally obtained diaphragm is 25 μm, and scanning electron microscope (SEM) photograph is as shown in Figure 5.From fig. 5, it can be seen that carbon
Sour calcium has uniformly been coated on chitin nano fibrous membrane, and resulting biomass nano fibre diaphragm has compact texture.
Embodiment 5
9g silica (granular size 100nm), 1g Kynoar-hexafluoropropylene copolymer and 50mL acetone is mixed
Conjunction stirs evenly, and obtains coating agent., for basement membrane, to be utilized on the chitin nano fibrous membrane of the resulting cyano of embodiment 2 modification
Dipping method coats one layer of coating agent in membrane surface.Obtain the chitin nanometer of the silicon dioxide coating of hygrometric state and cyano modification
Tunica fibrosa.Later by resulting chitin nano fibrous membrane at 70 DEG C, 1MPa carries out hot pressing, and the dry 12h at 70 DEG C, obtains later
To biomass nano fibre diaphragm.
The average thickness of finally obtained diaphragm is 25 μm, and scanning electron microscope (SEM) photograph is as shown in Figure 6.From fig. 6, it can be seen that two
Silica has uniformly been coated on chitin nano fibrous membrane, and resulting biomass nano fibre diaphragm has fine and close knot
Structure.
Embodiment 6
1g Kynoar-hexafluoropropylene copolymer and 50mL acetone are mixed evenly, coating agent is obtained.To implement
It is basement membrane on the chitin nano fibrous membrane of the resulting cyano of example 2 modification, using dipping method, coats one layer of coating in membrane surface
Agent.Obtain the chitin nano fibrous membrane of the Kynoar-hexafluoropropylene copolymer coating and cyano modification of hygrometric state.Later will
For resulting chitin nano fibrous membrane at 70 DEG C, 1MPa carries out hot pressing, and the dry 12h at 70 DEG C, obtains biomass nano later
Fibre diaphragm.
The average thickness of finally obtained diaphragm is 25 μm, and scanning electron microscope (SEM) photograph is as shown in Figure 7.From figure 7 it can be seen that poly-
Vinylidene fluoride-hexafluoropropylene copolymer has uniformly been coated on chitin nano fibrous membrane, and resulting biomass nano is fine
Tieing up diaphragm has compact texture.
7 electrochemical property test of embodiment
Embodiment 4, embodiment 5 and the finally obtained diaphragm of embodiment 6 are subjected to electrochemical property test, using following institute
The method stated, and commercial polypropylene lithium ion battery separator described earlier is as a comparison.
1) positive preparation
First by anode active material of phosphate iron lithium, conductive agent acetylene black, polyvinylidene fluoride (PVDF, number-average molecular weight
500000), to be uniformly mixed according to mass ratio 8:1:1, n-methyl-2-pyrrolidone is added, stirring forms uniform anode material
Slurry.
The slurry is uniformly coated on aluminium carbon foil, is dried under 100 DEG C of vacuum drying ovens, roll-in, punching, is put after weighing
It is spare in glove box.
2) preparation of battery
By anode obtained in 1) and diaphragm and lithium piece successively lamination, and (battery size 2032) is fitted into button cell.
The diaphragm obtains battery 1 when being the chitin nano fiber diaphragm of calcium carbonate coating in embodiment 4, the diaphragm is embodiment
Battery 2 is obtained in 5 when the chitin nano fiber diaphragm of silicon dioxide coating, the diaphragm is Kynoar-in embodiment 6
Battery 3 is obtained when the chitin nano fiber diaphragm of hexafluoropropylene copolymer coating, the diaphragm is commercial polypropylene lithium ion
Battery 4 is obtained when battery diaphragm.
By solvent be (ethylene carbonate (EC): methyl ethyl carbonate (EMC): dimethyl carbonate (DMC) volume ratio is 1:
Lithium hexafluoro phosphate (LiPF 1:1)6) electrolyte about 20 μ L be injected separately into above-mentioned battery 1-4, sealed cell shell obtains 4
2032 type lithium ion batteries.
3) battery long circulating is tested
At 25 ± 5 DEG C, battery 1-4 is subjected to constant current density (2C) charge and discharge, studies discharge capacity with charge and discharge
The variation of number.Test result as illustrated in figs. 8-11, it can be seen that composite diaphragm in embodiment 4, embodiment 5 and embodiment 6
The circulating battery capacity of (finally obtained diaphragm), is above commercial polypropylene lithium ion battery separator.
The biomass nano fiber composite diaphragm mechanical tensile strength of the coating of surface prepared by the present invention is high, electrochemistry
It can be excellent.
Embodiment 8
1) by the cellulose nano-fibrous paper pulp of 3g (source is that hundred million moral Food Co., Ltd of Hainan provides, and purity is food-grade)
It is dispersed in 1L deionized water, obtains suspension；Be added 12g sodium hydroxide, add 1L acrylonitrile solution (solvent is acetone,
Concentration is 1M), it is stirred at room temperature 5 hours.It filters, and is cleaned twice with acetone and deionized water respectively later, obtain 3g cyanogen
Base is modified cellulose nano-fibrous.
2) by gained cyano modify it is cellulose nano-fibrous be re-dispersed into deionized water, obtaining concentration is
The cellulose nano-fibrous slurries of the cyano modification of 0.3wt.%.The cellulose nano-fibrous slurries that resulting cyano is modified exist
Copy paper is carried out on paper machine, is then formed a film through dehydration, and the cellulose nano-fibrous membrane of the cyano modification of hygrometric state is obtained.Later to wet
The cellulose nano-fibrous membrane of the cyano modification of state is dried, and dry temperature is 70 DEG C, and time 12h obtains cyano and repairs
The cellulose nano-fibrous diaphragm of decorations.Its area is 1m2, with a thickness of 20 μm, scanning electron microscope (SEM) photograph is as shown in figure 12.It can be straight from Figure 12
See aperture very little possessed by the cellulose nano-fibrous diaphragm that ground finds out that the cyano of acquisition is modified, the i.e. resulting life of the present embodiment
Substance nano fiber diaphragm has compact texture.
Biomass nano fibre diaphragm described in the present embodiment has good mechanical strength, and ionic conductivity is high, with it
Lithium ion battery circulation volume for diaphragm preparation is higher.
As seen from the above embodiment, biomass nano fibre diaphragm provided by the invention includes the life that surface modification has cyano
Substance nanofiber film layer, with compact texture.In the present invention, due to the modification of cyano, biomass nano fibre diaphragm
Surface gel state can be formed in conjunction with liquid electrolyte, lithium ion can be transmitted by the gel state, so that lithium ion
Transmit the aperture independent of diaphragm.Biomass nano fibre diaphragm compactness provided by the invention is good and ionic conductivity
Height is higher than commercial polypropylene lithium ion battery separator using it as the lithium ion battery circulation volume of diaphragm preparation.The present invention avoids
Biomass nano fibre diaphragm will realize high porosity by pore-creating to improve many and diverse step of diaphragm lithium ion conductivity
Suddenly, biomass nano fibre diaphragm provided by the present application has good mechanical performance, and it is fine to realize fine and close biomass nano
Dimension diaphragm equally has the breakthrough of excellent electrochemical performance.
The above is only a preferred embodiment of the present invention, it is noted that for making the professional technique of the art
Personnel are that by various modifications to these embodiments without departing from the technical principles of the invention, and these
Modification also should be regarded as the range that the present invention should protect.
Claims (10)
1. a kind of biomass nano fibre diaphragm characterized by comprising the biomass nano tunica fibrosa with compact texture
Layer, the biomass nano fiber film layer have the biomass nano fiber of cyano to be made by chemical modification.
2. biomass nano fibre diaphragm according to claim 1, which is characterized in that the biomass nano fibre diaphragm
Further include: it is compounded in the coat of the biomass nano fiber film surface, the coat includes ceramic particle and polymerization
One of object is a variety of.
3. biomass nano fibre diaphragm according to claim 2, which is characterized in that the ceramic particle is selected from oxidation
One of aluminium, silica and calcium carbonate are a variety of；The polymer is selected from fluoropolymer, poly(aryl ether ketone), polyimides, gathers
One of methyl methacrylate and aromatic polysulfonamide are a variety of, and the fluoropolymer is preferably Kynoar, inclined fluorine
Ethylene-hexafluoropropylene copolymer, vinylidene-chlorotrifluoroethylcopolymer copolymer, vinylidene-trifluoro-ethylene copolymer, fluorination second
One of allyl alkene copolymer, ethylene tetrafluoroethylene copolymer and ethylene trichlorine fluoride copolymers are a variety of.
4. biomass nano fibre diaphragm according to claim 2, which is characterized in that the biomass nano fiber is selected from
One of cellulose nano-fibrous and chitin nanofiber is a variety of；The biomass nano fibre diaphragm with a thickness of 5-
500 μm, mechanical tensile strength 10MPa-300MPa.
5. a kind of preparation method of biomass nano fibre diaphragm, which comprises the following steps:
S1, biomass nano fiber slurry is provided；
S2, the biomass nano fiber slurry is reacted with dressing agent, the dressing agent is in acrylonitrile and different acrylonitrile
It is one or more, obtain the biomass nano fiber for being modified with cyano；
S3, the biomass nano fiber for being modified with cyano is subjected to copy paper, obtains biomass nano fibre diaphragm.
6. preparation method according to claim 5, which is characterized in that the step S1 specifically:
Biomass nano fiber and dispersion liquid are mixed, is beaten, obtains biomass nano fiber slurry；The biomass is received
Rice fiber is selected from one of cellulose nano-fibrous and chitin nanofiber or a variety of；The dispersion liquid is selected from water and ethyl alcohol
One of or it is a variety of；The mass percent concentration of the biomass nano fiber is 0.01-50%.
7. preparation method according to claim 5, which is characterized in that in the step S2, the reaction in initiator and
It is carried out under the conditions of cosolvent is existing；The initiator is selected from sodium hydroxide, hydrogen peroxide, ammonium ceric nitrate, iron ammonium sulfate, sulfuric acid
One of iron, potassium peroxydisulfate and ammonium persulfate are a variety of；The cosolvent is selected from one of ethyl alcohol, acetone and acetonitrile or more
Kind.
8. the preparation method according to any one of claim 5-7, which is characterized in that in the step S3, the copy paper
Obtain the biomass nano tunica fibrosa of hygrometric state；
The preparation method further includes step S4: carrying out surface painting on the biomass nano tunica fibrosa of the hygrometric state with coating agent
It covers, the coating agent includes solvent and coating ingredient, described to be applied as point including one of ceramic particle and polymer or more
Kind；Hot pressing and drying are carried out later, obtain biomass nano fibre diaphragm.
9. preparation method according to claim 8, which is characterized in that in the step S4, the solvent is selected from acetone, four
One of hydrogen furans, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide are a variety of；Hygrometric state after the surface coating
The pressure that biomass nano tunica fibrosa carries out hot pressing is 0.1MPa-80MPa, and temperature is 20 DEG C -100 DEG C.
10. biomass nano fibre diaphragm according to any one of claims 1-4 or claim 5-9 are described in any item
The biomass nano fibre diaphragm that preparation method obtains is preparing the application in lithium battery.
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