CN105826508B - Piezoelectric ceramics composite diaphragm, preparation method and lithium ion battery - Google Patents
Piezoelectric ceramics composite diaphragm, preparation method and lithium ion battery Download PDFInfo
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- CN105826508B CN105826508B CN201610366285.XA CN201610366285A CN105826508B CN 105826508 B CN105826508 B CN 105826508B CN 201610366285 A CN201610366285 A CN 201610366285A CN 105826508 B CN105826508 B CN 105826508B
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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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of piezoelectric ceramics composite diaphragm of present invention offer, preparation method and lithium ion battery, wherein preparation method, including：After dispersant dissolving is added in organic solvent or water, piezoelectric ceramic powder material is added and keeps piezoelectric ceramic powder material evenly dispersed in organic solvent or water, forms piezoelectric ceramic powder dispersion liquid；Binder and surfactant are added in the piezoelectric ceramic powder dispersion liquid, forms the coating fluid of piezoelectric ceramic powder；Surface single or double using the piezoelectric ceramic powder coating fluid in porous basement membrane coats Piezoelectric Ceramic Coatings, forms composite diaphragm；The composite diaphragm is polarised in the electric field, piezoelectric ceramics composite diaphragm is made.The present invention can improve the security performance and heavy-current discharge performance of lithium ion battery using the piezoelectric ceramics composite diaphragm, and lithium ion battery is enable to carry out self-charging in the case of compression.
Description
Technical field
The present invention relates to diaphragm and technical field of lithium ion more particularly to a kind of piezoelectric ceramics composite diaphragm, its systems
Preparation Method and lithium ion battery.
Background technology
Lithium ion battery has the characteristics that specific energy density is high, service life is long, memory-less effect and operating voltage are high, at
For the hot spot of novel power supply technical research in recent years.It is light-weight due to its energy density height, except being widely used in mobile phone, notebook etc.
Outside digital electronic goods, it is widely applied in recent years in electric tool, electric vehicle etc..
Common lithium ion battery is made of positive/negative material, electrolyte, diaphragm and battery case packaging material.Every
Film is the important component of lithium ion battery, and play prevents positive/negative short-circuit in the battery, while being carried in charge and discharge process
For the effect of ion transport channel, performance determines the interfacial structure of battery, internal resistance etc., directly affects the capacity of battery, follows
The characteristics such as ring performance and security performance, the diaphragm haveing excellent performance play an important role the comprehensive performance for improving battery.Mesh
Preceding lithium ion battery separator material is mainly polyalkene diaphragm material, including polyethylene (PE), polypropylene (PP) single layer microporous film,
PP/PE/PP three-layer composite microporous membranes and polyalkene diaphragm material surface coat Al2O3、SiO2It waits inorganic ceramic materials and gathers
The composite diaphragm of vinylidene (PVDF) and other polymer.
In consideration of it, how to provide a kind of piezoelectric ceramics composite diaphragm, preparation method and lithium ion battery, with improve lithium from
The security performance and heavy-current discharge performance of sub- battery, so that lithium ion battery is carried out self-charging in the case of compression becomes mesh
The preceding technical issues that need to address.
Invention content
In order to solve the above technical problems, the present invention provide a kind of piezoelectric ceramics composite diaphragm, preparation method and lithium from
Sub- battery can improve the security performance and heavy-current discharge performance of lithium ion battery, enable lithium ion battery in the feelings of compression
Self-charging is carried out under condition.
In a first aspect, the present invention provides a kind of preparation method of piezoelectric ceramics composite diaphragm, including：
After dispersant dissolving is added in organic solvent or water, piezoelectric ceramic powder material is added and makes piezoelectric ceramic powder
Material is evenly dispersed in organic solvent or water, forms piezoelectric ceramic powder dispersion liquid；
Binder and surfactant are added in the piezoelectric ceramic powder dispersion liquid, forms the painting of piezoelectric ceramic powder
Cloth liquid；
Surface single or double using the piezoelectric ceramic powder coating fluid in porous basement membrane coats Piezoelectric Ceramic Coatings,
Form composite diaphragm；
The composite diaphragm is polarised in the electric field, piezoelectric ceramics composite diaphragm is made.
Optionally, the method for making piezoelectric ceramic powder material evenly dispersed in organic solvent or water, including：Ball milling is ground
Mill；
And/or
Surface single or double using the piezoelectric ceramic powder coating fluid in porous basement membrane coats Piezoelectric Ceramic Coatings
Method, including：Dip-coating, blade coating or transfer；
And/or
The organic solvent, including but not limited to：Acetone, butanone, cyclohexanone, N-Methyl pyrrolidone, N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, toluene, acetic acid second
The composition of one or more of ester, n-hexane, hexamethylene；
And/or
The polarization process is that the composite diaphragm is placed in parallel-plate electric field in 0.5- at a temperature of 80-130 DEG C
Polarize 5-120min under the voltage of 5kV/mm, makes the electricdomain in Piezoelectric Ceramic Coatings along polarized electric field orientations.
Second aspect, the present invention provide a kind of piezoelectric ceramics composite diaphragm, and the piezoelectric ceramics composite diaphragm is by above-mentioned system
Preparation Method is made.
Optionally, the thickness of the porous basement membrane is 10-30um；
And/or
The thickness of the Piezoelectric Ceramic Coatings is 2-10um.
Optionally, the porous basement membrane is the monolayer polyethylene prepared using wet processing biaxial tension or super high molecular weight
Single-layer polypropylene seperation film or poly- prepared by polypropylene diaphragm or dry method simple tension prepared by polyethylene diagrams, dry method biaxial tension
Propylene/polyethylene/polypropylene sandwich diaphragm, the non-woven fabrics of polyester, glass fibre, the nonwoven prepared using electrical spinning method
Cloth.
Optionally, the Piezoelectric Ceramic Coatings are made of piezoelectric ceramic powder material, binder and auxiliary agent；The auxiliary agent,
Including but not limited to：Surfactant and dispersant.
Optionally, the piezoelectric ceramic powder material, including but not limited to：Barium titanate, lead titanate-zirconate, Modified Titanium zirconic acid
Lead, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum lead plumbate, modified lead titanate, lead titanates-lead magnesio-niobate；The piezoelectric ceramic powder
Weight content of the body material in the Piezoelectric Ceramic Coatings is 50-97%；
And/or
The binder, including but not limited to：Butadiene-styrene rubber, cellulose and its derivates, Kynoar, inclined fluorine second
Alkene-hexafluoropropylene copolymer, poly(aryl ether ketone), polyacrylic acid, polyacrylate and its derivative, polyacrylonitrile, acrylate-
Acrylonitrile copolymer, copolymer in cinnamic acrylic ester, polyoxyethylene ether, polysulfones, polytetrafluoroethylene (PTFE)；The binder is in institute
It is 3-20% to state the weight content in Piezoelectric Ceramic Coatings.
Optionally, weight content of the auxiliary agent in the Piezoelectric Ceramic Coatings is 0.05-5%；
And/or
The surfactant, including but not limited to：Stearate, oleate, lauryl sulfate, detergent alkylate
Sulfonate, dioctyl succinate disulfonate acid, liver sodium taurocholate etc., glycerin monostearate, polyoxyethylene ether, polyoxyethylene-polyoxy
Propylene copolymer, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether；
And/or
The dispersant, including but not limited to：Triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose
Derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, castor oil, glyceryl monostearate, three glycerol stearates
Ester, oleic acid acyl.
The third aspect, the present invention provide a kind of lithium ion battery, including：Positive plate, negative plate, electrolyte and positioned at anode
Diaphragm between piece and negative plate, the electrolyte fully infiltrate the positive plate, negative plate and diaphragm, which is characterized in that institute
It is above-mentioned piezoelectric ceramics composite diaphragm to state diaphragm.
Optionally, the electric domain orientation direction of Piezoelectric Ceramic Coatings and internal electric field direction phase in the piezoelectric ceramics composite diaphragm
Together；
And/or
The lithium ion battery is button cell, takeup type or Stackable batteries；
And/or
The outer packing of the lithium ion battery is rigid package or the flexible packaging of box hat；
And/or
The positive plate, including：One plus plate current-collecting body and the positive electrode material layer for being formed in the plus plate current-collecting body surface；
And/or
The negative plate, including：One negative current collector and the negative electrode material layer for being formed in the negative current collector surface；
And/or
Active material used in the positive electrode material layer, including：LiMn2O4, LiFePO4, cobalt acid lithium or nickle cobalt lithium manganate
Ternary composite cathode material；
And/or
Active material used in the negative electrode material layer, including：Artificial graphite, natural graphite, carbon nanotube or graphene.
As shown from the above technical solution, piezoelectric ceramics composite diaphragm, preparation method and lithium ion battery of the invention, energy
The security performance and heavy-current discharge performance for enough improving lithium ion battery, enable lithium ion battery to be carried out in the case of compression certainly
Charging.
Description of the drawings
Fig. 1 is a kind of flow diagram of the preparation method for piezoelectric ceramics composite diaphragm that one embodiment of the invention provides；
Fig. 2 is a kind of structural schematic diagram for piezoelectric ceramics composite diaphragm that one embodiment of the invention provides.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical solution in the embodiment of the present invention carries out clear, complete description, it is clear that described embodiment is only
It is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiment of the present invention, ordinary skill people
The every other embodiment that member is obtained without making creative work, shall fall within the protection scope of the present invention.
Fig. 1 shows a kind of preparation method for piezoelectric ceramics composite diaphragm that one embodiment of the invention provides, including step
101-104：
101, after dispersant dissolving is added in organic solvent or water, piezoelectric ceramic powder material is added and makes piezoelectric ceramics
Powder body material is evenly dispersed in organic solvent or water, forms piezoelectric ceramic powder dispersion liquid.
In a particular application, it can make piezoelectric ceramic powder material in organic solvent or water by the methods of ball milling or grinding
It is evenly dispersed.
In a particular application, the organic solvent, including but not limited to：Acetone, butanone, cyclohexanone, N- crassitudes
Ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, chloroform, dichloromethane, carbon tetrachloride, two chloroethenes
The composition of one or more of alkane, toluene, ethyl acetate, n-hexane, hexamethylene etc..
102, binder and surfactant are added in the piezoelectric ceramic powder dispersion liquid, forms piezoelectric ceramic powder
Coating fluid.
103, the surface single or double using the piezoelectric ceramic powder coating fluid in porous basement membrane coats piezoelectric ceramics
Coating forms composite diaphragm.
In a particular application, can be existed using the piezoelectric ceramic powder coating fluid by the methods of dip-coating, blade coating or transfer
The surface single or double of porous basement membrane coats Piezoelectric Ceramic Coatings.
104, the composite diaphragm is polarised in the electric field, piezoelectric ceramics composite diaphragm is made.
In a particular application, the polarization process is placed in the composite diaphragm parallel at a temperature of 80-130 DEG C
Plate electric field polarizes 5-120min under the voltage of 0.5-5kV/mm, and the electricdomain in Piezoelectric Ceramic Coatings is made to be orientated row along polarized electric field
Row.
Piezoelectric ceramics composite diaphragm made from the preparation method of the piezoelectric ceramics composite diaphragm of the present embodiment, can improve lithium
The security performance and heavy-current discharge performance of ion battery；The Piezoelectric Ceramic Coatings of piezoelectric ceramics composite diaphragm have than porous base
The higher heat resistance of film, it is short-circuit even if remaining to prevent the contact of positive and negative anodes in the case where basement membrane fuses；Simultaneously as pressure
The piezoelectric property of electroceramics coating, the electrostriction effect under electric field conditions can effectively inhibit the formation of cathode dendrite, into
One step improves the security performance of lithium ion battery；The built in field that Piezoelectric Ceramic Coatings are formed after polarization can promote lithium ion
Transmission, improve the discharge performance of lithium ion battery；The transmission of lithium ion can be realized using the piezoelectric effect of piezoceramics layer,
To be implemented without the self-charging under conditions of additional power source.
The embodiment of the present invention also provides a kind of piezoelectric ceramics composite diaphragm, and the piezoelectric ceramics composite diaphragm is as shown in Figure 1
Preparation method described in embodiment is made.
Manufactured piezoelectric ceramics composite diaphragm can be found in Fig. 2, in fig. 2, manufactured piezoelectric ceramics composite diaphragm, including：
Porous basement membrane 1 and the Piezoelectric Ceramic Coatings 2 by polarization process coated in the porous membrane surface single or double.
In a particular application, the thickness of the porous basement membrane 1 is 10-30um.
In a particular application, the thickness of the Piezoelectric Ceramic Coatings is 2-10um, and optimal is 3-6um.
In a particular application, the porous basement membrane 1 is the monolayer polyethylene prepared using wet processing biaxial tension or surpassed
Single-layer polypropylene prepared by polypropylene diaphragm or dry method simple tension prepared by High molecular weight polyethylene diaphragm, dry method biaxial tension
Diaphragm or polypropylene, polyethylene/polypropylene sandwich diaphragm, glass fibre, are prepared using electrical spinning method the non-woven fabrics of polyester
Non-woven fabrics.
In a particular application, the Piezoelectric Ceramic Coatings are made of piezoelectric ceramic powder material, binder and auxiliary agent；It is described
Auxiliary agent, including but not limited to：Surfactant and dispersant.
Further, the piezoelectric ceramic powder material, including but not limited to：Barium titanate, lead titanate-zirconate, Modified Titanium zirconic acid
Lead, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum lead plumbate, modified lead titanate, lead titanates-lead magnesio-niobate etc.；The piezoelectric ceramics
Weight content of the powder body material in the Piezoelectric Ceramic Coatings is 50-97%, and optimal is 70-95%.
Further, the binder, including but not limited to：Butadiene-styrene rubber, cellulose and its derivates, polyvinylidene fluoride
Alkene, vinylidene fluoride-hexafluoropropylene copolymer, poly(aryl ether ketone), polyacrylic acid, polyacrylate and its derivative, polyacrylonitrile,
Acrylic ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, polyoxyethylene ether, polysulfones, polytetrafluoroethylene (PTFE) etc.；Institute
It is 3-20% to state weight content of the binder in the Piezoelectric Ceramic Coatings, and optimal is 5-15%.
Further, weight content of the auxiliary agent in the Piezoelectric Ceramic Coatings is 0.05-5%, and optimal is 0.1-
4%.
Further, the surfactant, including but not limited to：Stearate, oleate, lauryl sulfate,
Dodecyl benzene sulfonate, dioctyl succinate disulfonate acid, liver sodium taurocholate etc., glycerin monostearate, polyoxyethylene ether, polyoxy
Ethylene-poiyoxypropylene copolymer, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene
Fatty alcohol ether etc.；
Further, the dispersant, including but not limited to：Triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methylpent
Alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, castor oil, glyceryl monostearate, three are firmly
Glycerol, oleic acid acyl etc..
The piezoelectric ceramics composite diaphragm of the present embodiment, as shown in Figure 1 the preparation method described in embodiment be made, piezoelectric ceramics
Coating has piezoelectric property by polarization process, can improve the security performance and heavy-current discharge performance of lithium ion battery；
The Piezoelectric Ceramic Coatings of piezoelectric ceramics composite diaphragm have heat resistance more higher than porous basement membrane, even if in the feelings of basement membrane fusing
Remain to prevent the contact of positive and negative anodes under condition and short-circuit；Simultaneously as the piezoelectric property of Piezoelectric Ceramic Coatings, under electric field conditions
Electrostriction effect can effectively inhibit the formation of cathode dendrite, further increase the security performance of lithium ion battery；Piezoelectricity is made pottery
The built in field that porcelain coating is formed after polarization can promote the transmission of lithium ion, improve the discharge performance of lithium ion battery；Profit
The transmission that lithium ion can be realized with the piezoelectric effect of piezoceramics layer, to be implemented without oneself under conditions of additional power source
Charging.
The embodiment of the present invention also provides a kind of lithium ion battery, including：Positive plate, negative plate, electrolyte and positioned at anode
Diaphragm between piece and negative plate, the electrolyte fully infiltrate the positive plate, negative plate and diaphragm；The diaphragm is above-mentioned
Piezoelectric ceramics composite diaphragm (structure of the piezoelectric ceramics composite diaphragm can be found in Fig. 2).
It should be noted that the piezoelectric ceramics composite diaphragm can be made up of preparation method described in Fig. 1 embodiments.
In a particular application, the electric domain orientation direction of Piezoelectric Ceramic Coatings and internal electric field in the piezoelectric ceramics composite diaphragm
Direction is identical.
In a particular application, the diaphragm be Fig. 2 embodiments described in piezoelectric ceramics composite diaphragm on the basis of, it is described
Lithium ion battery can be manufactured by the conventional method of state of the art；The lithium ion battery can be button cell, volume
Wound or Stackable batteries；The outer packing of the lithium ion battery can be rigid package or the flexible packaging of box hat.
In a particular application, the positive plate, including：One plus plate current-collecting body and it is formed in the plus plate current-collecting body surface
Positive electrode material layer；The negative plate, including：One negative current collector and the negative electrode material layer for being formed in the negative current collector surface.
Further, active material used in the positive electrode material layer, including：LiMn2O4, LiFePO4, cobalt acid lithium or nickel
Cobalt manganic acid lithium ternary composite cathode material etc..
Further, active material used in the negative electrode material layer, including：Artificial graphite, natural graphite, carbon nanotube
Or graphene etc..
The lithium ion battery of the present embodiment the advantage is that with higher battery safety and discharge performance, and
Self-charging can be carried out under conditions of bearing external pressure, solve energy requirement under emergency condition.The pressure of piezoelectric ceramics composite diaphragm
Electroceramics coating has heat resistance more higher than porous basement membrane, even if remaining to prevent positive and negative anodes in the case where basement membrane fuses
Contact and it is short-circuit；Simultaneously as the piezoelectric property of Piezoelectric Ceramic Coatings, the electrostriction effect under electric field conditions can be effective
The formation for inhibiting cathode dendrite, further increases the security performance of lithium ion battery；What Piezoelectric Ceramic Coatings were formed after polarization
Built in field can promote the transmission of lithium ion, improve the discharge performance of lithium ion battery；It is imitated using the piezoelectricity of piezoceramics layer
The transmission that should be able to realize lithium ion, to be implemented without the self-charging under conditions of additional power source.
In order to better illustrate the present invention, embodiment 1-12 and comparative example 1-2 are following provided, and pass through following test sides
Method tests embodiment 1-12 and comparative example 1-2, the test method, including：The volume test of battery charging and discharging recycle ratio,
Battery heat stability testing and pressure charging measurement；Wherein：
Battery charging and discharging recycle ratio volume test：Battery carries out charge and discharge cycles test at 0.1C to 2C different multiplyings,
Corresponding specific capacity is recorded respectively.
Battery heat stability testing：Battery is placed in 140 DEG C of oil baths and is heated, observes battery open circuit voltage variation in real time
Value records battery open circuit voltage values after 1h.
Pressure charging measurement：Pulse shock is applied to battery, while testing the open-circuit voltage values of battery, by 10min, note
Record cell output voltage value amplification.
Embodiment 1
(1) preparation of piezoelectric ceramics composite diaphragm：After neopelex 2g dissolvings are added in 300ml water, add
Enter 200g piezoelectric ceramics lead titanate-zirconate powder, keep lead titanate-zirconate evenly dispersed in water by ball milling, forms piezoelectric ceramics moisture
Dispersion liquid.Acrylic acid ester emulsion binder 20g, the lauryl sodium sulfate 5g of self-crosslinking are added in aqueous dispersions, it is evenly dispersed
Form piezoelectric ceramics coating fluid.Using intaglio plate transfer method by piezoelectric ceramics coating solution polypropylene diaphragm surface shape
At composite diaphragm.Composite diaphragm is polarized with the field strength of 1kV/mm at 80 DEG C 1h in flat field, it is compound that piezoelectric ceramics is made
Diaphragm.
(2) preparation of positive plate：By 85 parts of positive active material cobalt acid lithium, 5 parts of acetylene black, 5 parts of electrically conductive graphite, PVDF5
Part is uniformly mixed with solvent N-methyl pyrilidone, prepares anode sizing agent；Anode sizing agent is uniformly applied in aluminium foil current collection pole surface
After cloth drying, positive plate is made.
(3) preparation of negative plate：By 90.5 mass parts of negative electrode active material (graphite), 6 parts of acetylene black, carboxymethyl cellulose
1 part, 2.5 parts of butadiene-styrene rubber, uniformly mix in alcohol-water mixed solution, prepare negative electrode slurry.By negative electrode slurry in copper foil current collection
After the drying of pole surface even spread, negative plate is made.
(4) preparation of lithium ion battery：Between positive plate and negative plate, it is put into piezoelectric ceramics composite diaphragm, piezoelectricity pottery
The direction of porcelain coating electricdomain is identical as the direction of internal electric field, and the organic electrolyte of a concentration of 1M of lithium hexafluoro phosphate is added (in solvent
The volume ratio of ethylene carbonate methyl ethyl carbonate is 1：2) it, is put into reed compression, 2032 lithium ion battery of coin shape is made.
Embodiment 2
(1) preparation of piezoelectric ceramics composite diaphragm：After Sodium Polyacrylate 7.5g dissolvings are added in 300mL water, it is added
200g piezoelectric ceramics lead titanate-zirconate powder, keeps lead titanate-zirconate evenly dispersed in water by ball milling, and it is water-dispersed to form piezoelectric ceramics
Liquid.Butylbenzene binder 5g is added in aqueous dispersions, Qula leads to 3g, evenly dispersed formation piezoelectric ceramics coating fluid.Using coating
Piezoelectric ceramics coating solution is formed single side composite diaphragm by the method for stick blade coating on the surface of polypropylene diaphragm.By composite diaphragm
Polarized with the field strength of 1kV/mm at 80 DEG C 1h in flat field, and piezoelectric ceramics composite diaphragm is made.
(2) preparation of positive plate：By 85 parts of anode active material of phosphate iron lithium, 5 parts of acetylene black, 5 parts of electrically conductive graphite,
PVDF5 parts are uniformly mixed with solvent N-methyl pyrilidone, prepare anode sizing agent；By anode sizing agent in aluminium foil current collection pole surface
After even spread drying, positive plate is made.
(3) preparation of negative plate：By 90.5 mass parts of negative electrode active material (graphite), 6 parts of acetylene black, carboxymethyl cellulose
1 part, 2.5 parts of butadiene-styrene rubber, uniformly mix in alcohol-water mixed solution, prepare negative electrode slurry.By negative electrode slurry in copper foil current collection
After the drying of pole surface even spread, negative plate is made.
(4) preparation of lithium ion battery：Between positive plate and negative plate, it is put into piezoelectric ceramics composite diaphragm, piezoelectricity pottery
The direction of porcelain coating electricdomain is identical as the direction of internal electric field, and the organic electrolyte of a concentration of 1M of lithium hexafluoro phosphate is added (in solvent
The volume ratio of ethylene carbonate methyl ethyl carbonate is 1：1) it, is put into reed compression, 2032 lithium ion battery of coin shape is made.
Embodiment 3
Embodiment 1 is repeated, unlike：Piezoelectric ceramic powder materials'use barium titanate 150g.
Embodiment 4
Embodiment 1 is repeated, unlike：After Sodium Polyacrylate 5g dissolvings are added in 300mL acetone, 200g titanium zirconiums are added
Lead plumbate (piezoelectric ceramic powder material) forms piezoelectric ceramics acetone dispersion liquor.
Embodiment 5
Embodiment 1 is repeated, unlike：Piezoelectric ceramics composite diaphragm is double spread.
Embodiment 6
Embodiment 1 is repeated, unlike：The temperature of polarization process is 110 DEG C, and flat field field strength is 3kV/mm.
Embodiment 7
Embodiment 1 is repeated, unlike：Binder uses poly(aryl ether ketone) 20g.
Embodiment 8
Embodiment 2 is repeated, unlike：Organic solvent uses n,N-dimethylacetamide 300mL, using phase inversion method poly-
It forms a film on propylene diaphragm.
Embodiment 9
Embodiment 2 is repeated, unlike：Binder uses the acetone soln 50g of 10wt%PVDF.
Embodiment 10
Embodiment 2 is repeated, unlike：Dispersant is castor oil 3g.
Embodiment 11
Embodiment 2 is repeated, unlike：Piezoelectric ceramic powder materials'use lead meta-columbute 200g.
Embodiment 12
Embodiment 2 is repeated, unlike：Binder uses hydroxymethyl cellulose 15g.
Comparative example 1 (prior art)
Embodiment 1 is repeated, unlike：Diaphragm uses polypropylene diaphragm.
Comparative example 2 (prior art)
Embodiment 1 is repeated, unlike：Diaphragm uses PVDF diaphragms.
Embodiment 1-12 and comparative example 1-2 are tested by above-mentioned test method, obtained piezoelectric ceramics it is compound every
The test result of the performance of film and battery is as shown in table 1.
Table 1
It is compound using the piezoelectric ceramics of the embodiment of the present invention by table 1 it is found that compared with the prior art (comparative example 1 and 2)
Lithium ion battery made from diaphragm has higher battery safety and discharge performance.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of piezoelectric ceramics composite diaphragm, which is characterized in that including：
After dispersant dissolving is added in organic solvent or water, piezoelectric ceramic powder material is added and makes piezoelectric ceramic powder material
It is evenly dispersed in organic solvent or water, form piezoelectric ceramic powder dispersion liquid；
Binder and surfactant are added in the piezoelectric ceramic powder dispersion liquid, forms the coating of piezoelectric ceramic powder
Liquid；
Surface single or double using the piezoelectric ceramic powder coating fluid in porous basement membrane coats Piezoelectric Ceramic Coatings, is formed
Composite diaphragm；
The composite diaphragm is polarised in the electric field, piezoelectric ceramics composite diaphragm is made；
Wherein, the piezoelectric ceramic powder material, including：Barium titanate, lead titanate-zirconate, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum
Lead plumbate, modified lead titanate；Weight content of the piezoelectric ceramic powder material in the Piezoelectric Ceramic Coatings is 50-97%；
The lead titanate-zirconate, including：Modified lead titanate-zirconate；The modified lead titanate, including：Lead titanates-lead magnesio-niobate.
2. preparation method according to claim 1, which is characterized in that make piezoelectric ceramic powder material in organic solvent or water
In evenly dispersed method, including：Ball milling or grinding；
And/or
The side of Piezoelectric Ceramic Coatings is coated in the surface single or double of porous basement membrane using the piezoelectric ceramic powder coating fluid
Method, including：Dip-coating, blade coating or transfer；
And/or
The organic solvent, including：Acetone, butanone, cyclohexanone, N-Methyl pyrrolidone, N,N-dimethylformamide, N, N- bis-
Methylacetamide, tetrahydrofuran, chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, toluene, ethyl acetate, n-hexane, hexamethylene
The composition of one or more of alkane；
And/or
The polarization process is that the composite diaphragm is placed in parallel-plate electric field in 0.5-5kV/mm at a temperature of 80-130 DEG C
Voltage under polarize 5-120min, make the electricdomain in Piezoelectric Ceramic Coatings along polarized electric field orientations.
3. a kind of piezoelectric ceramics composite diaphragm, which is characterized in that the piezoelectric ceramics composite diaphragm is by any in claim 1-2
Preparation method described in is made.
4. piezoelectric ceramics composite diaphragm according to claim 3, which is characterized in that the thickness of the porous basement membrane is 10-
30μm；
And/or
The thickness of the Piezoelectric Ceramic Coatings is 2-10 μm.
5. piezoelectric ceramics composite diaphragm according to claim 3, which is characterized in that the porous basement membrane is using wet method work
The polypropylene diaphragm of monolayer polyethylene or ultra-high molecular weight polyethylene diaphragm, dry method biaxial tension preparation prepared by skill biaxial tension
Dry method simple tension prepare single-layer polypropylene seperation film or polypropylene, polyethylene/polypropylene sandwich diaphragm, polyester nonwoven
Cloth, glass fibre, the non-woven fabrics prepared using electrical spinning method.
6. piezoelectric ceramics composite diaphragm according to claim 3, which is characterized in that the Piezoelectric Ceramic Coatings are made pottery by piezoelectricity
Porcelain powder body material, binder and auxiliary agent composition；The auxiliary agent, including：Surfactant and dispersant.
7. piezoelectric ceramics composite diaphragm according to claim 6, which is characterized in that the binder, including：Butylbenzene rubber
Glue, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, poly(aryl ether ketone), polyacrylic acid, gathers cellulose and its derivates
Acrylate and its derivative, acrylic ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, gather polyacrylonitrile
Ethylene oxide ether, polysulfones, polytetrafluoroethylene (PTFE)；Weight content of the binder in the Piezoelectric Ceramic Coatings is 3-20%.
8. piezoelectric ceramics composite diaphragm according to claim 6, which is characterized in that the auxiliary agent is applied in the piezoelectric ceramics
Weight content in layer is 0.05-5%；
And/or
The surfactant, including：It is stearate, oleate, lauryl sulfate, dodecyl benzene sulfonate, two pungent
Base sodium sulfosuccinate, liver sodium taurocholate, glycerin monostearate, polyoxyethylene ether, Pluronic F68, fat
Fat acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether；
And/or
The dispersant, including：Triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, poly- third
Acrylamide, guar gum, fatty acid polyethylene glycol ester, castor oil, glyceryl monostearate, glyceryl tristearate, oleic acid acyl.
9. a kind of lithium ion battery, including：Positive plate, negative plate, electrolyte and the diaphragm between positive plate and negative plate,
The electrolyte fully infiltrates the positive plate, negative plate and diaphragm, which is characterized in that the diaphragm is in claim 3-8
Any one of them piezoelectric ceramics composite diaphragm.
10. lithium ion battery according to claim 9, which is characterized in that piezoelectricity is made pottery in the piezoelectric ceramics composite diaphragm
The electric domain orientation direction of porcelain coating is identical as internal electric field direction；
And/or
The lithium ion battery is button cell, takeup type or Stackable batteries；
And/or
The outer packing of the lithium ion battery is rigid package or the flexible packaging of box hat；
And/or
The positive plate, including：One plus plate current-collecting body and the positive electrode material layer for being formed in the plus plate current-collecting body surface；
And/or
The negative plate, including：One negative current collector and the negative electrode material layer for being formed in the negative current collector surface；
And/or
Active material used in the positive electrode material layer, including：LiMn2O4, LiFePO4, cobalt acid lithium or nickle cobalt lithium manganate ternary
Composite positive pole；
And/or
Active material used in the negative electrode material layer, including：Artificial graphite, natural graphite, carbon nanotube or graphene.
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