CN105826508A - Piezoelectric ceramic composite membrane, preparation method thereof and lithium ion battery - Google Patents
Piezoelectric ceramic composite membrane, preparation method thereof and lithium ion battery Download PDFInfo
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- CN105826508A CN105826508A CN201610366285.XA CN201610366285A CN105826508A CN 105826508 A CN105826508 A CN 105826508A CN 201610366285 A CN201610366285 A CN 201610366285A CN 105826508 A CN105826508 A CN 105826508A
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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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Abstract
The invention provides a piezoelectric ceramic composite membrane, a preparation method thereof and a lithium ion battery .The preparation method includes the steps of adding a dispersing agent to organic solvent or water to be dissolved, adding a piezoelectric ceramic powder material to be evenly dispersed in organic solvent or water to form piezoelectric ceramic powder dispersion liquid, adding an adhesive and a surface active agent to the piezoelectric ceramic powder dispersion liquid to form piezoelectric ceramic powder coating liquid, coating a single surface or double surfaces of a porous base membrane with piezoelectric ceramic coatings through the piezoelectric ceramic powder coating liquid to form a composite membrane, and polarizing the composite membrane in an electric field to prepare the piezoelectric ceramic composite membrane .By means of the piezoelectric ceramic composite membrane, the safety performance and large-current discharge performance of the lithium ion battery can be improved, and self-charging of the lithium ion battery can be achieved under voltage.
Description
Technical field
The present invention relates to barrier film and technical field of lithium ion, particularly relate to a kind of piezoelectric ceramics composite diaphragm, its preparation method and lithium ion battery.
Background technology
Lithium ion battery has specific energy density height, length in service life, memory-less effect and running voltage high, becomes the focus of novel power supply technical research in recent years.Owing to its energy density is high, lightweight, in addition to being widely used in the digital electronic goods such as mobile phone, notebook, in recent years obtain in electric tool, electric motor car etc. and be widely applied.
Common lithium ion battery is made up of positive/negative material, electrolyte, barrier film and battery case packaging material.Barrier film is the important component part of lithium ion battery, play in the battery and prevent positive/negative short circuit, the effect of ion transport channel is provided in charge and discharge process simultaneously, its performance determines the interfacial structure of battery, internal resistance etc., directly affecting the characteristics such as the capacity of battery, cycle performance and security performance, the barrier film of excellent performance has important effect to the combination property improving battery.Lithium ion battery separator material is mainly polyalkene diaphragm material at present, including polyethylene (PE), polypropylene (PP) single layer microporous film, PP/PE/PP three-layer composite microporous membrane and coats Al at polyalkene diaphragm material surface2O3、SiO2Deng inorganic ceramic material and Kynoar (PVDF) and the composite diaphragm of other polymer.
Given this, how a kind of piezoelectric ceramics composite diaphragm, its preparation method and lithium ion battery are provided, to improve security performance and the heavy-current discharge performance of lithium ion battery, making lithium ion battery can carry out self-charging in the case of pressurized becomes to be presently required and solves the technical problem that.
Summary of the invention
For solving above-mentioned technical problem, the present invention provides a kind of piezoelectric ceramics composite diaphragm, its preparation method and lithium ion battery, it is possible to improves security performance and the heavy-current discharge performance of lithium ion battery, makes lithium ion battery can carry out self-charging in the case of pressurized.
First aspect, the present invention provides the preparation method of a kind of piezoelectric ceramics composite diaphragm, including:
After adding dispersant dissolving in organic solvent or water, add piezoelectric ceramic powder material and also make piezoelectric ceramic powder material dispersed in organic solvent or water, form piezoelectric ceramic powder dispersion liquid；
In described piezoelectric ceramic powder dispersion liquid, add binding agent and surfactant, form the coating fluid of piezoelectric ceramic powder；
Utilize described piezoelectric ceramic powder coating fluid at the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane, form composite diaphragm；
Described composite diaphragm is carried out in the electric field polarization process, prepares piezoelectric ceramics composite diaphragm.
Alternatively, make piezoelectric ceramic powder material homodisperse method in organic solvent or water, including: ball milling or grinding；
And/or,
Utilize described piezoelectric ceramic powder coating fluid in the method for the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane, including: dip-coating, scratch or transfer；
And/or,
Described organic solvent, include but not limited to: acetone, butanone, Ketohexamethylene, N-Methyl pyrrolidone, N, the compositions of one or more in dinethylformamide, N,N-dimethylacetamide, oxolane, chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, toluene, ethyl acetate, normal hexane, hexamethylene；
And/or,
It is at a temperature of 80-130 DEG C that described polarization processes, and described composite diaphragm is placed in parallel-plate electric field and polarizes under the voltage of 0.5-5kV/mm 5-120min, make the electricdomain in Piezoelectric Ceramic Coatings along polarized electric field orientations.
Second aspect, the present invention provides a kind of piezoelectric ceramics composite diaphragm, and described piezoelectric ceramics composite diaphragm is made up of above-mentioned preparation method.
Alternatively, the thickness of described porous basement membrane is 10-30um；
And/or,
The thickness of described Piezoelectric Ceramic Coatings is 2-10um.
Alternatively, described porous basement membrane is the polypropylene diaphragm using the monolayer polyethylene prepared of wet processing biaxial tension or ultra-high molecular weight polyethylene barrier film, dry method biaxial tension to prepare or prepared by dry method simple tension single-layer polypropylene barrier film or polypropylene, polyethylene/polypropylene sandwich diaphragm, the non-woven fabrics of polyester, glass fibre, the non-woven fabrics that utilizes electrical spinning method to prepare.
Alternatively, described Piezoelectric Ceramic Coatings is made up of piezoelectric ceramic powder material, binding agent and auxiliary agent；Described auxiliary agent, includes but not limited to: surfactant and dispersant.
Alternatively, described piezoelectric ceramic powder material, include but not limited to: Barium metatitanate., lead titanate-zirconate, Modified Titanium lead zirconates, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum lead plumbate, modified lead titanate, lead titanates-lead magnesio-niobate；Described piezoelectric ceramic powder material weight content in described Piezoelectric Ceramic Coatings is 50-97%；
And/or,
Described binding agent, includes but not limited to: butadiene-styrene rubber, cellulose and its derivates, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, PAEK, polyacrylic acid, polyacrylate and derivant thereof, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, polyoxyethylene ether, polysulfones, politef；Described binding agent weight content in described Piezoelectric Ceramic Coatings is 3-20%.
Alternatively, described auxiliary agent weight content in described Piezoelectric Ceramic Coatings is 0.05-5%；
And/or,
Described surfactant, includes but not limited to: stearate, oleate, lauryl sulfate, dodecyl benzene sulfonate, dioctyl succinate disulfonate acid, liver sodium cholate etc., glyceryl monostearate, polyoxyethylene ether, Pluronic F68, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether；
And/or,
Described dispersant, includes but not limited to: triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, Oleum Ricini, glycerol monostearate, glyceryl tristearate, oleic acid acyl.
The third aspect, the present invention provides a kind of lithium ion battery, including: positive plate, negative plate, electrolyte and the barrier film between positive plate and negative plate, described electrolyte fully infiltrates described positive plate, negative plate and barrier film, it is characterized in that, described barrier film is above-mentioned piezoelectric ceramics composite diaphragm.
Alternatively, in described piezoelectric ceramics composite diaphragm, the electric domain orientation direction of Piezoelectric Ceramic Coatings is identical with internal electric field direction；
And/or,
Described lithium ion battery is button cell, takeup type or Stackable batteries；
And/or,
The outer package of described lithium ion battery is rigid package or the flexible packaging of box hat；
And/or,
Described positive plate, including a: plus plate current-collecting body and the positive electrode material layer that is formed at described anode collection surface；
And/or,
Described negative plate, including a: negative current collector and the negative electrode material layer that is formed at this negative pole currect collecting surface；
And/or,
Active material used in described 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 described negative electrode material layer, including: Delanium, native graphite, CNT or Graphene.
As shown from the above technical solution, piezoelectric ceramics composite diaphragm, its preparation method and the lithium ion battery of the present invention, it is possible to improve security performance and the heavy-current discharge performance of lithium ion battery, makes lithium ion battery can carry out self-charging in the case of pressurized.
Accompanying drawing explanation
The schematic flow sheet of the preparation method of a kind of piezoelectric ceramics composite diaphragm that Fig. 1 provides for one embodiment of the invention；
The structural representation of a kind of piezoelectric ceramics composite diaphragm that Fig. 2 provides for one embodiment of the invention.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with the accompanying drawing in the embodiment of the present invention, technical scheme in the embodiment of the present invention is carried out clear, complete description, obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on embodiments of the invention, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
Fig. 1 shows the preparation method of a kind of piezoelectric ceramics composite diaphragm that one embodiment of the invention provides, including step 101-104:
101, after adding dispersant dissolving in organic solvent or water, add piezoelectric ceramic powder material and also make piezoelectric ceramic powder material dispersed in organic solvent or water, form piezoelectric ceramic powder dispersion liquid.
In a particular application, can by the method such as ball milling or grinding make piezoelectric ceramic powder material in organic solvent or water dispersed.
In a particular application, described organic solvent, include but not limited to: acetone, butanone, Ketohexamethylene, N-Methyl pyrrolidone, N, the compositions of one or more in dinethylformamide, N,N-dimethylacetamide, oxolane, chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, toluene, ethyl acetate, normal hexane, hexamethylene etc..
102, in described piezoelectric ceramic powder dispersion liquid, add binding agent and surfactant, form the coating fluid of piezoelectric ceramic powder.
103, utilize described piezoelectric ceramic powder coating fluid at the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane, form composite diaphragm.
In a particular application, dip-coating can be passed through, scratch or the method such as transfer, utilize described piezoelectric ceramic powder coating fluid at the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane.
104, described composite diaphragm is carried out in the electric field polarization process, prepare piezoelectric ceramics composite diaphragm.
In a particular application, it is at a temperature of 80-130 DEG C that described polarization processes, and described composite diaphragm is placed in parallel-plate electric field and polarizes under the voltage of 0.5-5kV/mm 5-120min, make the electricdomain in Piezoelectric Ceramic Coatings along polarized electric field orientations.
The piezoelectric ceramics composite diaphragm that the preparation method of the piezoelectric ceramics composite diaphragm of the present embodiment prepares, it is possible to improve security performance and the heavy-current discharge performance of lithium ion battery；The Piezoelectric Ceramic Coatings of piezoelectric ceramics composite diaphragm has more higher heat resistance than porous basement membrane, short-circuit even if remaining to prevent the contact of both positive and negative polarity in the case of basement membrane fuses；Simultaneously as the piezoelectric property of Piezoelectric Ceramic Coatings, the electrostriction effect under electric field conditions can effectively suppress the formation of negative pole dendrite, improves the security performance of lithium ion battery further；The built in field that Piezoelectric Ceramic Coatings is formed after polarization can promote the transmission of lithium ion, improves the discharge performance of lithium ion battery；The piezoelectric effect utilizing piezoceramics layer is capable of the transmission of lithium ion, thus the self-charging under conditions of being implemented without additional power source.
The embodiment of the present invention also provides for a kind of piezoelectric ceramics composite diaphragm, and the preparation method described in described piezoelectric ceramics composite diaphragm embodiment as shown in Figure 1 is made.
The piezoelectric ceramics composite diaphragm made can be found in Fig. 2, in fig. 2, and the piezoelectric ceramics composite diaphragm made, including: porous basement membrane 1 and the Piezoelectric Ceramic Coatings 2 processed through polarization in the coating of described porous membrane surface single or double.
In a particular application, the thickness of described porous basement membrane 1 is 10-30um.
In a particular application, the thickness of described Piezoelectric Ceramic Coatings is 2-10um, and optimum is 3-6um.
In a particular application, described porous basement membrane 1 is the polypropylene diaphragm using the monolayer polyethylene prepared of wet processing biaxial tension or ultra-high molecular weight polyethylene barrier film, dry method biaxial tension to prepare or prepared by dry method simple tension single-layer polypropylene barrier film or polypropylene, polyethylene/polypropylene sandwich diaphragm, the non-woven fabrics of polyester, glass fibre, the non-woven fabrics that utilizes electrical spinning method to prepare.
In a particular application, described Piezoelectric Ceramic Coatings is made up of piezoelectric ceramic powder material, binding agent and auxiliary agent；Described auxiliary agent, includes but not limited to: surfactant and dispersant.
Further, described piezoelectric ceramic powder material, include but not limited to: Barium metatitanate., lead titanate-zirconate, Modified Titanium lead zirconates, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum lead plumbate, modified lead titanate, lead titanates-lead magnesio-niobate etc.；Described piezoelectric ceramic powder material weight content in described Piezoelectric Ceramic Coatings is 50-97%, and optimum is 70-95%.
Further, described binding agent, includes but not limited to: butadiene-styrene rubber, cellulose and its derivates, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, PAEK, polyacrylic acid, polyacrylate and derivant thereof, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, polyoxyethylene ether, polysulfones, politef etc.；Described binding agent weight content in described Piezoelectric Ceramic Coatings is 3-20%, and optimum is 5-15%.
Further, described auxiliary agent weight content in described Piezoelectric Ceramic Coatings is 0.05-5%, and optimum is 0.1-4%.
Further, described surfactant, includes but not limited to: stearate, oleate, lauryl sulfate, dodecyl benzene sulfonate, dioctyl succinate disulfonate acid, liver sodium cholate etc., glyceryl monostearate, polyoxyethylene ether, Pluronic F68, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether etc.；
Further, described dispersant, includes but not limited to: triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, Oleum Ricini, glycerol monostearate, glyceryl tristearate, oleic acid acyl etc..
The piezoelectric ceramics composite diaphragm of the present embodiment, the preparation method described in embodiment is made as shown in Figure 1, and Piezoelectric Ceramic Coatings processes through polarization and has piezoelectric property, it is possible to improve security performance and the heavy-current discharge performance of lithium ion battery；The Piezoelectric Ceramic Coatings of piezoelectric ceramics composite diaphragm has more higher heat resistance than porous basement membrane, short-circuit even if remaining to prevent the contact of both positive and negative polarity in the case of basement membrane fuses；Simultaneously as the piezoelectric property of Piezoelectric Ceramic Coatings, the electrostriction effect under electric field conditions can effectively suppress the formation of negative pole dendrite, improves the security performance of lithium ion battery further；The built in field that Piezoelectric Ceramic Coatings is formed after polarization can promote the transmission of lithium ion, improves the discharge performance of lithium ion battery；The piezoelectric effect utilizing piezoceramics layer is capable of the transmission of lithium ion, thus the self-charging under conditions of being implemented without additional power source.
The embodiment of the present invention also provides for a kind of lithium ion battery, including: positive plate, negative plate, electrolyte and the barrier film between positive plate and negative plate, described electrolyte fully infiltrates described positive plate, negative plate and barrier film；Described barrier film is above-mentioned piezoelectric ceramics composite diaphragm (structure of this piezoelectric ceramics composite diaphragm can be found in Fig. 2).
It should be noted that described piezoelectric ceramics composite diaphragm can be made by preparation method described in Fig. 1 embodiment.
In a particular application, in described piezoelectric ceramics composite diaphragm, the electric domain orientation direction of Piezoelectric Ceramic Coatings is identical with internal electric field direction.
In a particular application, described barrier film be described in Fig. 2 embodiment piezoelectric ceramics composite diaphragm on the basis of, described lithium ion battery can be by the traditional method manufacture of state of the art；Described lithium ion battery can be button cell, takeup type or Stackable batteries；The outer package of described lithium ion battery can be rigid package or the flexible packaging of box hat.
In a particular application, described positive plate, including a: plus plate current-collecting body and the positive electrode material layer that is formed at described anode collection surface；Described negative plate, including a: negative current collector and the negative electrode material layer that is formed at this negative pole currect collecting surface.
Further, active material used in described positive electrode material layer, including: LiMn2O4, LiFePO4, cobalt acid lithium or nickle cobalt lithium manganate ternary composite cathode material etc..
Further, active material used in described negative electrode material layer, including: Delanium, native graphite, CNT or Graphene etc..
The lithium ion battery of the present embodiment, has an advantage in that have higher battery safety and discharge performance, and can carry out self-charging under conditions of bearing external pressure, solves energy requirement under emergency condition.The Piezoelectric Ceramic Coatings of piezoelectric ceramics composite diaphragm has more higher heat resistance than porous basement membrane, short-circuit even if remaining to prevent the contact of both positive and negative polarity in the case of basement membrane fuses；Simultaneously as the piezoelectric property of Piezoelectric Ceramic Coatings, the electrostriction effect under electric field conditions can effectively suppress the formation of negative pole dendrite, improves the security performance of lithium ion battery further；The built in field that Piezoelectric Ceramic Coatings is formed after polarization can promote the transmission of lithium ion, improves the discharge performance of lithium ion battery；The piezoelectric effect utilizing piezoceramics layer is capable of the transmission of lithium ion, thus the self-charging under conditions of being implemented without additional power source.
In order to better illustrate the present invention, following provide embodiment 1-12 and comparative example 1-2, and by following method of testing, embodiment 1-12 and comparative example 1-2 are tested, described method of testing, including: battery charging and discharging recycle ratio volume test, battery heat stability testing and pressure filling electrical testing；Wherein:
Battery charging and discharging recycle ratio volume test: battery carries out charge and discharge cycles test under 0.1C to 2C different multiplying, records corresponding specific capacity respectively.
Battery heat stability testing: battery is placed in 140 DEG C of oil baths heating, real-time monitored battery open circuit voltage changing value, battery open circuit voltage values after record 1h.
Pressure filling electrical testing: battery is applied pulse shock, tests the open-circuit voltage values of battery simultaneously, through 10min, records cell output voltage value amplification.
Embodiment 1
(1) preparation of piezoelectric ceramics composite diaphragm: in 300ml water add dodecylbenzene sodium sulfonate 2g dissolve after, add 200g piezoelectric ceramics lead titanate-zirconate powder, by ball milling make lead titanate-zirconate in water dispersed, formed piezoelectric ceramics aqueous dispersions.Acrylic acid ester emulsion binding agent 20g, the sodium lauryl sulphate 5g of self-crosslinking, dispersed formation piezoelectric ceramics coating fluid is added in aqueous dispersions.Piezoelectric ceramics coating solution is formed composite diaphragm by the method using intaglio plate transfer on the surface of polypropylene diaphragm.By composite diaphragm in flat field with the field intensity of 1kV/mm at 80 DEG C of 1h that polarize, prepare piezoelectric ceramics composite diaphragm.
(2) preparation of positive plate: positive active material cobalt acid lithium 85 parts, acetylene black 5 parts, electrically conductive graphite 5 parts, PVDF5 part are uniformly mixed with solvent N-methyl pyrilidone, prepares anode sizing agent；By anode sizing agent after aluminium foil colelctor electrode surface even spread is dried, prepare positive plate.
(3) preparation of negative plate: by negative active core-shell material (graphite) 90.5 mass parts, acetylene black 6 parts, carboxymethyl cellulose 1 part, butadiene-styrene rubber 2.5 parts, uniformly mix in alcohol-water mixed solution, prepare cathode size.By cathode size after Copper Foil colelctor electrode surface even spread is dried, prepare negative plate.
(4) preparation of lithium ion battery: between positive plate and negative plate, put into piezoelectric ceramics composite diaphragm, the direction of Piezoelectric Ceramic Coatings electricdomain is identical with the direction of internal electric field, add the organic electrolyte (in solvent, the volume ratio of ethylene carbonate Ethyl methyl carbonate is 1:2) that hexafluorophosphoric acid lithium concentration is 1M, put into reed to compress, make coin shape 2032 lithium ion battery.
Embodiment 2
(1) preparation of piezoelectric ceramics composite diaphragm: in 300mL water add sodium polyacrylate 7.5g dissolve after, add 200g piezoelectric ceramics lead titanate-zirconate powder, by ball milling make lead titanate-zirconate in water dispersed, formed piezoelectric ceramics aqueous dispersions.Butylbenzene binding agent 5g, TritonX 3g, dispersed formation piezoelectric ceramics coating fluid is added in aqueous dispersions.Piezoelectric ceramics coating solution is formed one side composite diaphragm by the method using spreading rod blade coating on the surface of polypropylene diaphragm.By composite diaphragm in flat field with the field intensity of 1kV/mm at 80 DEG C of 1h that polarize, prepare piezoelectric ceramics composite diaphragm.
(2) preparation of positive plate: anode active material of phosphate iron lithium 85 parts, acetylene black 5 parts, electrically conductive graphite 5 parts, PVDF5 part are uniformly mixed with solvent N-methyl pyrilidone, prepares anode sizing agent；By anode sizing agent after aluminium foil colelctor electrode surface even spread is dried, prepare positive plate.
(3) preparation of negative plate: by negative active core-shell material (graphite) 90.5 mass parts, acetylene black 6 parts, carboxymethyl cellulose 1 part, butadiene-styrene rubber 2.5 parts, uniformly mix in alcohol-water mixed solution, prepare cathode size.By cathode size after Copper Foil colelctor electrode surface even spread is dried, prepare negative plate.
(4) preparation of lithium ion battery: between positive plate and negative plate, put into piezoelectric ceramics composite diaphragm, the direction of Piezoelectric Ceramic Coatings electricdomain is identical with the direction of internal electric field, add the organic electrolyte (in solvent, the volume ratio of ethylene carbonate Ethyl methyl carbonate is 1:1) that hexafluorophosphoric acid lithium concentration is 1M, put into reed to compress, make coin shape 2032 lithium ion battery.
Embodiment 3
Repeat embodiment 1, except for the difference that: piezoelectric ceramic powder materials'use Barium metatitanate. 150g.
Embodiment 4
Repeat embodiment 1, except for the difference that: after adding sodium polyacrylate 5g dissolving in 300mL acetone, add 200g lead titanate-zirconate (piezoelectric ceramic powder material) and form piezoelectric ceramics acetone dispersion liquor.
Embodiment 5
Repeat embodiment 1, except for the difference that: piezoelectric ceramics composite diaphragm is double spread.
Embodiment 6
Repeat embodiment 1, except for the difference that: the temperature that polarization processes is 110 DEG C, and flat field field intensity is 3kV/mm.
Embodiment 7
Repeat embodiment 1, except for the difference that: binding agent uses PAEK 20g.
Embodiment 8
Repeat embodiment 2, except for the difference that: organic solvent uses N,N-dimethylacetamide 300mL, use phase inversion method film forming on polypropylene diaphragm.
Embodiment 9
Repeat embodiment 2, except for the difference that: binding agent uses the acetone soln 50g of 10wt%PVDF.
Embodiment 10
Repeat embodiment 2, except for the difference that: dispersant is Oleum Ricini 3g.
Embodiment 11
Repeat embodiment 2, except for the difference that: piezoelectric ceramic powder materials'use lead meta-columbute 200g.
Embodiment 12
Repeat embodiment 2, except for the difference that: binding agent uses hydroxymethyl cellulose 15g.
Comparative example 1 (prior art)
Repeat embodiment 1, except for the difference that: barrier film uses polypropylene diaphragm.
Comparative example 2 (prior art)
Repeat embodiment 1, except for the difference that: barrier film uses PVDF barrier film.
Being tested embodiment 1-12 and comparative example 1-2 by above-mentioned method of testing, the piezoelectric ceramics composite diaphragm obtained and the test result of the performance of battery are as shown in table 1.
Table 1
By table 1, compared with prior art (comparative example 1 and 2), the lithium ion battery utilizing the piezoelectric ceramics composite diaphragm of the embodiment of the present invention to prepare has higher battery safety and discharge performance.
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；Although the present invention being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or the most some or all of technical characteristic is carried out equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the preparation method of a piezoelectric ceramics composite diaphragm, it is characterised in that including:
After adding dispersant dissolving in organic solvent or water, add piezoelectric ceramic powder material and also make piezoelectric ceramic powder material dispersed in organic solvent or water, form piezoelectric ceramic powder dispersion liquid；
In described piezoelectric ceramic powder dispersion liquid, add binding agent and surfactant, form the coating fluid of piezoelectric ceramic powder；
Utilize described piezoelectric ceramic powder coating fluid at the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane, form composite diaphragm；
Described composite diaphragm is carried out in the electric field polarization process, prepares piezoelectric ceramics composite diaphragm.
Preparation method the most according to claim 1, it is characterised in that make piezoelectric ceramic powder material homodisperse method in organic solvent or water, including: ball milling or grinding；
And/or,
Utilize described piezoelectric ceramic powder coating fluid in the method for the surface single or double coating Piezoelectric Ceramic Coatings of porous basement membrane, including: dip-coating, scratch or transfer；
And/or,
Described organic solvent, include but not limited to: acetone, butanone, Ketohexamethylene, N-Methyl pyrrolidone, N, the compositions of one or more in dinethylformamide, N,N-dimethylacetamide, oxolane, chloroform, dichloromethane, carbon tetrachloride, dichloroethanes, toluene, ethyl acetate, normal hexane, hexamethylene；
And/or,
It is at a temperature of 80-130 DEG C that described polarization processes, and described composite diaphragm is placed in parallel-plate electric field and polarizes under the voltage of 0.5-5kV/mm 5-120min, make the electricdomain in Piezoelectric Ceramic Coatings along polarized electric field orientations.
3. a piezoelectric ceramics composite diaphragm, it is characterised in that described piezoelectric ceramics composite diaphragm is made up of the preparation method according to any one of claim 1-2.
Piezoelectric ceramics composite diaphragm the most according to claim 3, it is characterised in that the thickness of described porous basement membrane is 10-30um；
And/or,
The thickness of described Piezoelectric Ceramic Coatings is 2-10um.
Piezoelectric ceramics composite diaphragm the most according to claim 3, it is characterized in that, described porous basement membrane is the polypropylene diaphragm using the monolayer polyethylene prepared of wet processing biaxial tension or ultra-high molecular weight polyethylene barrier film, dry method biaxial tension to prepare or prepared by dry method simple tension single-layer polypropylene barrier film or polypropylene, polyethylene/polypropylene sandwich diaphragm, the non-woven fabrics of polyester, glass fibre, the non-woven fabrics that utilizes electrical spinning method to prepare.
Piezoelectric ceramics composite diaphragm the most according to claim 3, it is characterised in that described Piezoelectric Ceramic Coatings is made up of piezoelectric ceramic powder material, binding agent and auxiliary agent；Described auxiliary agent, includes but not limited to: surfactant and dispersant.
Piezoelectric ceramics composite diaphragm the most according to claim 3, it is characterized in that, described piezoelectric ceramic powder material, includes but not limited to: Barium metatitanate., lead titanate-zirconate, Modified Titanium lead zirconates, lead meta-columbute, lead niobate barium-lithium, titanium zirconium lanthanum lead plumbate, modified lead titanate, lead titanates-lead magnesio-niobate；Described piezoelectric ceramic powder material weight content in described Piezoelectric Ceramic Coatings is 50-97%；
And/or,
Described binding agent, includes but not limited to: butadiene-styrene rubber, cellulose and its derivates, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, PAEK, polyacrylic acid, polyacrylate and derivant thereof, polyacrylonitrile, acrylic ester-acrylonitrile copolymer, copolymer in cinnamic acrylic ester, polyoxyethylene ether, polysulfones, politef；Described binding agent weight content in described Piezoelectric Ceramic Coatings is 3-20%.
Piezoelectric ceramics composite diaphragm the most according to claim 6, it is characterised in that described auxiliary agent weight content in described Piezoelectric Ceramic Coatings is 0.05-5%；
And/or,
Described surfactant, includes but not limited to: stearate, oleate, lauryl sulfate, dodecyl benzene sulfonate, dioctyl succinate disulfonate acid, liver sodium cholate etc., glyceryl monostearate, polyoxyethylene ether, Pluronic F68, fatty acid sorbitol ester, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether；
And/or,
Described dispersant, includes but not limited to: triethyl group hexyl phosphoric acid, sodium lauryl sulphate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, Oleum Ricini, glycerol monostearate, glyceryl tristearate, oleic acid acyl.
9. a lithium ion battery, including: positive plate, negative plate, electrolyte and the barrier film between positive plate and negative plate, described electrolyte fully infiltrates described positive plate, negative plate and barrier film, it is characterized in that, described barrier film is the piezoelectric ceramics composite diaphragm according to any one of claim 3-8.
Lithium ion battery the most according to claim 9, it is characterised in that in described piezoelectric ceramics composite diaphragm, the electric domain orientation direction of Piezoelectric Ceramic Coatings is identical with internal electric field direction；
And/or,
Described lithium ion battery is button cell, takeup type or Stackable batteries；
And/or,
The outer package of described lithium ion battery is rigid package or the flexible packaging of box hat；
And/or,
Described positive plate, including a: plus plate current-collecting body and the positive electrode material layer that is formed at described anode collection surface；
And/or,
Described negative plate, including a: negative current collector and the negative electrode material layer that is formed at this negative pole currect collecting surface；
And/or,
Active material used in described 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 described negative electrode material layer, including: Delanium, native graphite, CNT or Graphene.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61295678A (en) * | 1985-06-25 | 1986-12-26 | Japan Gore Tex Inc | Manufacture of piezoelectric film |
| CN102242464A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院理化技术研究所 | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof |
| CN103000954A (en) * | 2012-11-09 | 2013-03-27 | 国家纳米科学中心 | Energy pack |
| CN105273444A (en) * | 2014-07-23 | 2016-01-27 | 乐凯胶片股份有限公司 | Slurry composition and lithium ion battery diaphragm containing same |
-
2016
- 2016-05-27 CN CN201610366285.XA patent/CN105826508B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61295678A (en) * | 1985-06-25 | 1986-12-26 | Japan Gore Tex Inc | Manufacture of piezoelectric film |
| CN102242464A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院理化技术研究所 | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof |
| CN103000954A (en) * | 2012-11-09 | 2013-03-27 | 国家纳米科学中心 | Energy pack |
| CN105273444A (en) * | 2014-07-23 | 2016-01-27 | 乐凯胶片股份有限公司 | Slurry composition and lithium ion battery diaphragm containing same |
Non-Patent Citations (2)
| Title |
|---|
| YAN ZHANG ET AL: ""PVDF-PZT nanocomposite film based self-charging power cell"", 《NANOTECHNOLOGY》 * |
| 胡志宇 等: ""无机复合锂离子电池隔膜的制备及性能研究"", 《高分子学报》 * |
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