CN106159157B - A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application - Google Patents
A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application Download PDFInfo
- Publication number
- CN106159157B CN106159157B CN201510172322.9A CN201510172322A CN106159157B CN 106159157 B CN106159157 B CN 106159157B CN 201510172322 A CN201510172322 A CN 201510172322A CN 106159157 B CN106159157 B CN 106159157B
- Authority
- CN
- China
- Prior art keywords
- polymer composite
- composite diaphragm
- nano
- ceramics polymer
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
The invention discloses a kind of preparation methods of ceramics polymer composite diaphragm, are included in high-gravity rotating bed and prepare nano-ceramic particle presoma, depressurize presoma filter later, and vacuum drying is ground up, sieved, and calcine, obtain nano-ceramic particle；Binder is added in solvent and is dissolved, is later added thereto nano-ceramic particle obtained, ball milling, ceramic film slurry is obtained；Ceramic film slurry obtained is covered on basilar memebrane, ceramics polymer composite diaphragm is obtained.Diaphragm of the invention is strong to the wetability of electrolyte, and thermal stability is good, solves dusting problems present in existing ceramic diaphragm.
Description
Technical field
The invention belongs to electrochemical fields.More particularly, to a kind of ceramics polymer composite diaphragm preparation method, should
Ceramics polymer composite diaphragm and its application.
Background technique
Compared with the secondary cells such as traditional lead-acid accumulator, nickel-cadmium cell, nickel-hydrogen cell, lithium ion battery has single
Body cell voltage height, light weight, memory-less effect, pollution-free, self discharge is small, the advantages that having extended cycle life, and is that most development is latent
The battery of power.
Lithium ion battery is generally made of four anode, electrolyte, diaphragm and cathode parts.Lithium ion battery separator is to set
One layer of porous film material between anode and battery cathode, its effect mainly prevent positive and negative electrode active matter upright
It contacts and causes internal short-circuit of battery.The structure and performance of lithium ion battery separator determine the interfacial structure of battery, internal resistance
Deng having will greatly affect the performance of battery, energy and power density, cycle life and security performance including battery.
Currently, the lithium ion battery separator of commercialization is mainly the polyalkene diaphragm based on polythene PE, polypropylene PP,
Including single layer PE, single layer PP and three layers of PP/PE/PP composite membrane.But current polyalkene diaphragm comes with some shortcomings, a side
The compatibility of face, polyolefine material and electrolyte is poor, causes liquid absorption amount small, to affect the internal resistance of cell.In addition, polyolefin material
The lim-ited temperature stability of material, PE film can melt at 120-130 DEG C, and PP film can melt at 150-160 DEG C.
In addition, also disclosing a kind of Ceramic Composite diaphragm in the prior art, it is by superfine ceramic particle coated on porous
A kind of perforated film of substrate material surface, ceramic particle used are generally the oxide powder of nanometer or sub-micron, such as Al2O3,
SiO2, TiO2Deng.But existing commercialization Ceramic Composite diaphragm there are problems that " losing powder ", i.e., due to ceramic particle and base material
Adhesive force it is limited, cause ceramic particle to be detached from base material in use, this picking phenomenon will affect ceramic diaphragm in lithium
Service performance in ion battery.
Therefore, it is necessary to a kind of new lithium ion battery separators, it is good with the compatibility of electrolyte, and thermal stability is good and does not deposit
" picking " the problem of.
Summary of the invention
The first purpose of this invention is to provide a kind of preparation method of ceramics polymer composite diaphragm.
Second object of the present invention is to provide ceramics polymer composite diaphragm made from the above method.
Third object of the present invention is to provide the application of above-mentioned ceramics polymer composite diaphragm.
In order to achieve the above first purpose, the present invention adopts the following technical solutions：
A kind of preparation method of ceramics polymer composite diaphragm, includes the following steps：
1) nano-ceramic particle is prepared
Firstly, preparing presoma in high-gravity rotating bed using coprecipitation；Wherein, the concentration of inorganic salts is 0.2-
The concentration of 5mol/l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the concentration of dispersing agent is the 1-10% of the concentration of precipitating reagent
(w/w), the feed rate of inorganic salts is 10-500ml/min, and the feed rate of precipitating reagent is 10-500ml/min, hypergravity rotation
The revolving speed of rotated bed is 500-3000r/min, and reaction temperature is -20 DEG C -80 DEG C；
Secondly, presoma is carried out decompression suction filtration, it is small that 12-48 is dried in vacuo under the conditions of 40-80 DEG C after suction filtration object washing
When, it is ground up, sieved, is calcined 1-10 hours under the conditions of 500-1500 DEG C, it is 1-5 DEG C/h that heating rate is controlled in calcining, is received
Rice ceramic particle；
2) ceramic film slurry is prepared
Binder is added in solvent and is dissolved, is later added thereto nano-ceramic particle made from step 1), ball
Mill 2-10 hours, obtains ceramic film slurry；
3) ceramics polymer composite diaphragm is prepared
Ceramics film slurry made from step 2) is covered on basilar memebrane, ceramics polymer composite diaphragm is obtained,
The material of the basilar memebrane is polymer material.
Further, in step 1), nano-ceramic particle obtained is inorganic oxide, selected from silica, three oxidations
One or more mixtures of two aluminium, titanium dioxide, zirconium dioxide.Inorganic salts, precipitating reagent can refer to the prior art.Example
Such as, when nano-ceramic particle is silica, inorganic salts are sodium metasilicate, and precipitating reagent is ammonium carbonate；When nano-ceramic particle is
When aluminum oxide, inorganic salts are aluminum nitrate, and precipitating reagent is ammonium hydrogen carbonate or ammonium carbonate；When nano-ceramic particle is titanium dioxide
When, inorganic salts are metatitanic acid, and precipitating reagent is urea；When nano-ceramic particle is zirconium dioxide, inorganic salts are zirconium nitrate, precipitating
Agent is glycerine.The dosage of inorganic salts and precipitating reagent meets its reaction ratio, and is preferred so that precipitating reagent is slightly excessive.
Further, in step 1), the concentration of inorganic salts is 0.2-2mol/l, and the concentration of precipitating reagent is 1-5mol/l, point
Powder is PEG, and the concentration of dispersing agent is the 1-5% of precipitant concentration (w/w), and the feed rate of inorganic salts is 10-50ml/min,
The feed rate of precipitating reagent is 50-100ml/min, and high-gravity rotating bed revolving speed is 1500-2500r/min, reaction temperature 0
℃-50℃.Under this optimum condition, the partial size for the nano-ceramic particle being prepared is smaller, and particle diameter distribution is more evenly.
In step 1), filters object and be first washed with deionized, use ethanol washing again later.
Further, in step 1), being ground up, sieved is the product grinding obtained after drying, crosses the sieve of 250 mesh later.It grinds
Mill is to break up soft-agglomerated particle, prevents from generating bulk hard aggregation particle when calcining.
Further, in step 2), the binder is Kynoar and/or acrylic acid；The solvent be selected from acetone,
One or more kinds of mixtures of N,N-dimethylformamide (DMF), dimethyl acetamide (DMAC).
Further, in step 2), the mass ratio of the nano-ceramic particle and binder is 1-2：1, the binder
Ratio with solvent is 1g/30ml-2g/30ml.Control the ratio and binder and solvent of nano-ceramic particle and binder
Ratio be in order to guarantee ceramic film slurry can uniformly in polymeric substrate film preferably dispersion covering, will not be because too dense
And disperse uneven, it will not cause adhesive force not enough due to too dilute and then fall off.
Further, in step 2), when ball milling, drum's speed of rotation 100-400r/min.
Further, in step 3), the polymer material is polyethylene, polypropylene, Kynoar or polyvinyl alcohol.
Further, in step 3), ceramics film slurry made from step 2) is covered with roller coating, blade coating or Best-Effort request
It covers on basilar memebrane.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions：
Ceramics polymer composite diaphragm prepared by the above method, including：Basement membrane layer and basement membrane layer two sides
Ceramic coating；
The material of the basement membrane layer is polymer material；
The ceramic coating is that nano-ceramic particle is bonded to basement membrane layer surface to obtain；
In the ceramic coating, series connection forms consecutive structure between nano-ceramic particle, and ceramic coating presents hollow netted
Structure.Consecutive structure refers to that nano-ceramic particle is connected with each other between two or more, but not at block-like structure, it
Presence make ceramic coating show hollow reticular structure.
Further, the nano-ceramic particle is to be prepared according to the following steps to obtain：
Firstly, preparing presoma in high-gravity rotating bed using coprecipitation；Wherein, the concentration of inorganic salts is 0.2-
The concentration of 5mol/l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the concentration of dispersing agent is the 1-10% of the concentration of precipitating reagent
(w/w), the feed rate of inorganic salts is 10-500ml/min, and the feed rate of precipitating reagent is 10-500ml/min, hypergravity rotation
The revolving speed of rotated bed is 500-3000r/min, and reaction temperature is -20 DEG C -80 DEG C；
Secondly, presoma is carried out decompression suction filtration, it is small that 12-48 is dried in vacuo under the conditions of 40-80 DEG C after suction filtration object washing
When, it is ground up, sieved, is calcined 1-10 hours under the conditions of 500-1500 DEG C, it is 1-5 DEG C/h that heating rate is controlled in calcining, is received
Rice ceramic particle；
It is further, described that nano-ceramic particle is bonded to basement membrane layer surface is to follow the steps below：
Binder is added in solvent and is dissolved, is later added thereto nano-ceramic particle obtained, ball milling 2-10
Hour, obtain ceramic film slurry；
Ceramic film slurry obtained is covered on basilar memebrane, ceramic coating is formed, obtain ceramics polymer it is compound every
Film,
The material of the basilar memebrane is polymer material.
Further, the nano-ceramic particle is inorganic oxide, is selected from silica, aluminum oxide, titanium dioxide
One or more mixtures of titanium, zirconium dioxide.Inorganic salts, precipitating reagent can refer to the prior art.For example, when nanometer is made pottery
When porcelain particle is silica, inorganic salts are sodium metasilicate, and precipitating reagent is ammonium carbonate；When nano-ceramic particle is aluminum oxide
When, inorganic salts are aluminum nitrate, and precipitating reagent is ammonium hydrogen carbonate；When nano-ceramic particle is titanium dioxide, inorganic salts are metatitanic acid,
Precipitating reagent is urea；When nano-ceramic particle is zirconium dioxide, inorganic salts are zirconium nitrate, and precipitating reagent is glycerine.
Further, when preparing presoma in high-gravity rotating bed using coprecipitation, the concentration of inorganic salts is 0.2-
The concentration of 2mol/l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the concentration of dispersing agent is the 1-5% (w/ of precipitant concentration
W), the feed rate of inorganic salts is 10-50ml/min, and the feed rate of precipitating reagent is 50-100ml/min, high-gravity rotating bed
Revolving speed be 1500-2500r/min, reaction temperature be 0 DEG C -50 DEG C.Under this optimum condition, the nano ceramics that is prepared
The partial size of grain is smaller, and particle diameter distribution is more evenly.
It filters object to be first washed with deionized, uses ethanol washing again later.
Further, being ground up, sieved is the product grinding obtained after drying, crosses the sieve of 250 mesh later.Grinding is will be soft
Agglomerated particle is broken up, and prevents from generating bulk hard aggregation particle when calcining.
Further, the binder is Kynoar and/or acrylic acid；The solvent is selected from acetone, N, N- diformazan
One or more kinds of mixtures of base formamide (DMF), dimethyl acetamide (DMAC).
Further, the mass ratio of the nano-ceramic particle and binder is 1-2：1, the ratio of the binder and solvent
Example is 1g/30ml-2g/30ml.Control nano-ceramic particle and the ratio and binder of binder and the ratio of solvent be for
Guarantee ceramic film slurry can the uniformly preferably dispersion covering in polymeric substrate film, will not disperse not due to too dense
, it will not cause adhesive force not enough due to too dilute and then fall off.
Further, when ball milling, drum's speed of rotation 100-400r/min.
Further, the polymer material is polyethylene, polypropylene, Kynoar or polyvinyl alcohol.
Further, ceramic film slurry is covered on basilar memebrane with roller coating, blade coating or Best-Effort request.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions：
The application of above-mentioned ceramics polymer composite diaphragm, can be used as lithium ion battery separator.
Beneficial effects of the present invention are as follows：
1, the present invention is by with high-gravity rotating bed, using coprecipitation, control inorganic salts, precipitating reagent concentration, into
Material rate, reaction temperature and calcination condition prepare the nano-ceramic particle with special consecutive structure, in coating procedure
Hollow netted ceramic coating can be formed, effective low porosity for improving coat improves wetting of the diaphragm to electrolyte
Property the experiment has found that electrolyte can be realized on diaphragm of the invention and be sprawled；
2, of the invention to improve in terms of thermal stability：30min is heated at 150 DEG C, shrinking percentage is only 5%；
Temperature is improved to 30min is heated at 160 DEG C, shrinking percentage is only 10%.
3, since the nano-ceramic particle that the present invention uses has special consecutive structure, so that ceramic powder particle and bonding
The combination of agent is stronger, solves the problems, such as " picking " present in existing ceramic diaphragm.
4, preparation method of the invention has preparation time short, and at low cost, strong operability is reproducible, it is easy to accomplish
The characteristics of industrialized production.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 is the structural schematic diagram of ceramics polymer composite diaphragm of the invention.
Fig. 2 is the high-gravity rotating bed structural schematic diagram that the present invention uses.
Fig. 3 is transmission (TEM) photo of nano-ceramic particle made from embodiment 1.
Fig. 4 is profile scanning (SEM) photo of ceramics polymer composite diaphragm made from embodiment 1, wherein lower-left is base
Counterdie, upper right are ceramic coating.
Fig. 5 is that (a is substrate to contact angle photo of the electrolyte to the ceramics polymer composite membrane in basilar memebrane and embodiment 1
Film；B is the ceramics polymer composite membrane of embodiment 1).
Fig. 6 is that (a-c is basilar memebrane, and d-f is for the ceramics polymer composite membrane heating front and back photo of basilar memebrane and embodiment 1
The ceramics polymer composite membrane of embodiment 1；A, d are before heating, and after b, e are 150 DEG C of heating 30min, c, f are 160 DEG C of heating
After 30min).
Fig. 7 be in comparative example 1 and 2 gained nano-ceramic particle SEM photograph (a be comparative example 1 in gained nano ceramics
The SEM photograph of grain；B is the SEM photograph of gained nano-ceramic particle in comparative example 2).
Fig. 8 is that (a is comparative example 1 to contact angle photo of the electrolyte to the ceramics polymer composite membrane in comparative example 1,2 and 3
Ceramics polymer composite membrane；B is the ceramics polymer composite membrane of comparative example 2；C is that the ceramics polymer of comparative example 3 is compound
Film).
Fig. 9 is that (a-c is that the ceramics of comparative example 1 are poly- to photo before and after the ceramics polymer composite membrane of comparative example 1,2 and 3 heats
Object composite membrane is closed, d-f is the ceramics polymer composite membrane of comparative example 2, and g-i is the ceramics polymer composite membrane of comparative example 3；a,d,
G, before heating, b, e, after h is 150 DEG C of heating 30min, c, f, after i is 160 DEG C of heating 30min).
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1
The preparation method of above-mentioned ceramics polymer composite diaphragm, includes the following steps：
1) nano-ceramic particle is prepared
Firstly, presoma is prepared in high-gravity rotating bed using coprecipitation；Wherein, inorganic salts select Al
(NO3)3, concentration 0.3mol/l；Precipitating reagent selects (NH4)2CO3, concentration 2mol/l；Dispersing agent is PEG2000, dispersing agent
Concentration is 2% (w/w) of the concentration of precipitating reagent；The feed rate of inorganic salts is 30ml/min；The feed rate of precipitating reagent is
50ml/min；High-gravity rotating bed revolving speed 2500r/min, reaction temperature are 0 DEG C；
Secondly, presoma is carried out decompression suction filtration, filters object and be washed with deionized, ethanol washing is used again later, 70
It is dried in vacuo 24 hours, is ground up, sieved under the conditions of DEG C, calcined 2 hours under the conditions of 1200 DEG C, it is 2 that heating rate is controlled in calcining
DEG C/h, obtain aluminium oxide nano ceramic particle；
2) ceramics polymer composite diaphragm is prepared
Kynoar is added in acetone and is dissolved, A is obtained；
Aluminium oxide nano ceramic particle obtained is added in A, B is obtained；
B is carried out ball milling 2 hours, ceramic film slurry is obtained；
One layer of ceramic film slurry is coated respectively in the two sides of polypropylene-base bottom membrane with the method for Best-Effort request, is obtained
Ceramics polymer composite diaphragm is made in ceramic coating.
The mass ratio of the aluminium oxide nano ceramic particle powder and binder Kynoar is 1.5:1, the bonding
The ratio of agent Kynoar and solvent acetone is 1g：30ml.
The drum's speed of rotation is 350r/min.
Fig. 1 is the structural schematic diagram of ceramics polymer composite diaphragm of the invention.
Fig. 2 is the high-gravity rotating bed structural schematic diagram that the present invention uses.High-gravity rotating bed is the prior art, is answered
It has also been disclosed with method, details are not described herein.
Fig. 3 is transmission (TEM) photo of nano-ceramic particle made from embodiment 1.
Fig. 4 is profile scanning (SEM) photo of ceramics polymer composite diaphragm made from embodiment 1, and wherein lower-left is base
Bottom membrane, upper right are ceramic coating.As can be seen that due to the special consecutive structure of nano-ceramic powder used, so that ceramics apply
Hollow reticular structure is presented in layer, has larger porosity.
It is multiple to ceramics polymer prepared by basilar memebrane and embodiment 1 with contact angle measurement measurement lithium-ion battery electrolytes
Close the contact angle of film.The lithium salts of electrolyte used is lithium hexafluoro phosphate (LiPF6), concentration 1M, the composition and ratio of organic solvent
For：Ethylene carbonate (EC)：Dimethyl carbonate (DMC)：Methyl ethyl carbonate (EMC)=1：1：1.Fig. 5 is electrolyte to basilar memebrane
With the contact angle photo of the ceramics polymer composite membrane of embodiment 1.A is basilar memebrane, and the angle of wetting to electrolyte is 35.9 °；B is
The ceramics polymer composite diaphragm of embodiment 1 can be observed electrolyte and realize on ceramics polymer composite diaphragm to sprawl, can
See that Ceramic Composite diaphragm prepared by embodiment 1 is very good to the wettability of electrolyte, this may be the pottery due to embodiment 1
Porcelain coating has larger porosity.
Basilar memebrane and obtained Ceramic Composite diaphragm are put into vacuum oven, heat 30 points at different temperatures
Clock, concrete outcome are as shown in Figure 6.In figure, a, b, c are basilar memebrane, and d, e, f is the ceramics polymer composite membrane of embodiment 1；a,d
Before heating, after b, e are 150 DEG C of heating 30min, after c, f are 160 DEG C of heating 30min.As can be seen that being heated at 150 DEG C
After 30min, basilar memebrane shrinking percentage is 10%, and the ceramics polymer composite membrane shrinking percentage of embodiment 1 is 5%；Add at 160 DEG C
After hot 30min, basilar memebrane shrinking percentage is 30%, and partial vitrification phenomenon occurs, and the ceramics polymer of embodiment 1 is compound
Film shrinking percentage is 10%, and does not occur vitrification phenomenon.As can be seen that the ceramics polymer composite membrane of embodiment 1 is compared to base
Counterdie has apparent raising in terms of thermal stability.
It by the ceramics polymer composite membrane curling of embodiment 1 or folds or wipes, seen whether that substance is fallen.Experiment hair
Existing, there is no falling.It is believed that may special consecutive structure existing for the nano-ceramic particle as made from embodiment 1,
And coating forms the mode of ceramic coating and makes the combination of ceramic powder and binder, basilar memebrane stronger, so that it is not deposited
In " picking " problem of existing commercial ceramic diaphragm.
The application of the ceramics polymer composite diaphragm of embodiment 1 is used as lithium ion battery separator.
Embodiment 2
The preparation method of above-mentioned ceramics polymer composite diaphragm, includes the following steps：
1) nano-ceramic particle is prepared
Firstly, presoma is prepared in high-gravity rotating bed using coprecipitation；Wherein, inorganic salts select silicic acid
Sodium, concentration 0.2mol/l；Precipitating reagent selects ammonium carbonate, concentration 1mol/l；Dispersing agent is PEG2000, the concentration of dispersing agent
For 1% (w/w) of the concentration of precipitating reagent；The feed rate of inorganic salts is 10ml/min；The feed rate of precipitating reagent is 50ml/
min；High-gravity rotating bed revolving speed 1500r/min, reaction temperature are 50 DEG C；
Secondly, presoma is carried out decompression suction filtration, filters object and be washed with deionized, ethanol washing is used again later, 40
It is dried in vacuo 12 hours, is ground up, sieved under the conditions of DEG C, calcined 1 hour under the conditions of 500 DEG C, it is 1 that heating rate is controlled in calcining
DEG C/h, obtain nano-ceramic particle；
2) ceramics polymer composite diaphragm is prepared
Acrylic acid is added in n,N-Dimethylformamide and is dissolved, A is obtained；
Nano-ceramic particle obtained is added in A, B is obtained；
B is carried out ball milling 10 hours, ceramic film slurry is obtained；
One layer of ceramic film slurry is coated respectively in the two sides of polyvinyl bottom membrane with the method for blade coating, obtains ceramics
Ceramics polymer composite diaphragm is made in coating.
The mass ratio of the nano-ceramic particle powder and binder acrylic acid is 1:1, the binder acrylic acid and molten
The ratio of agent N,N-dimethylformamide is 2g：30ml.
The drum's speed of rotation is 100r/min.
After tested, the property of the ceramics polymer composite diaphragm obtained is similar to Example 1.
Embodiment 3
The preparation method of above-mentioned ceramics polymer composite diaphragm, includes the following steps：
1) nano-ceramic particle is prepared
Firstly, presoma is prepared in high-gravity rotating bed using coprecipitation；Wherein, inorganic salts select inclined titanium
Acid, concentration 2mol/l；Precipitating reagent selects urea, concentration 5mol/l；Dispersing agent is PEG2000, and the concentration of dispersing agent is heavy
5% (w/w) of the concentration of shallow lake agent；The feed rate of inorganic salts is 50ml/min；The feed rate of precipitating reagent is 100ml/min；
High-gravity rotating bed revolving speed 2500r/min, reaction temperature are 25 DEG C；
Secondly, presoma is carried out decompression suction filtration, filters object and be washed with deionized, ethanol washing is used again later, 80
It is dried in vacuo 48 hours, is ground up, sieved under the conditions of DEG C, calcined 10 hours under the conditions of 1500 DEG C, heating rate is controlled in calcining is
5 DEG C/h, obtain nano-ceramic particle；
2) ceramics polymer composite diaphragm is prepared
Acrylic acid is added in dimethyl acetamide and is dissolved, A is obtained；
Nano-ceramic particle obtained is added in A, B is obtained；
B is carried out ball milling 5 hours, ceramic film slurry is obtained；
One layer of ceramic film slurry is coated respectively in the two sides of polyvinyl alcohol basement membrane layer with the method for roller coating, is made pottery
Ceramics polymer composite diaphragm is made in porcelain coating.
The mass ratio of the nano-ceramic particle powder and binder acrylic acid is 1:1, the binder acrylic acid and molten
The ratio of agent dimethyl acetamide is 1.5g：30ml.
The drum's speed of rotation is 400r/min.
After tested, the property of the ceramics polymer composite diaphragm obtained is similar to Example 1.
Embodiment 4
With embodiment 1, difference is, inorganic salts are zirconium nitrate, and precipitating reagent is glycerine.Presoma is subjected to decompression pumping
Filter, is dried in vacuo 24 hours under the conditions of 60 DEG C, ground 250 mesh after filtering object washing, and it is small that 5 are calcined under the conditions of 1000 DEG C
When, control heating rate is 3 DEG C/h in calcining, obtains nano-ceramic particle.After tested, the ceramics polymer composite diaphragm obtained
Property it is similar to Example 1.
Embodiment 5
With embodiment 1, difference is, the concentration of inorganic salts is 5mol/l, and the concentration of precipitating reagent is 5mol/l, and dispersing agent is
PEG, the concentration of dispersing agent are 10% (w/w) of the concentration of precipitating reagent, and the feed rate of inorganic salts is 500ml/min, precipitating reagent
Feed rate be 500ml/min, high-gravity rotating bed revolving speed be 500r/min, reaction temperature be 40 DEG C.
Embodiment 6
With embodiment 1, difference is, the concentration of inorganic salts is 2.5mol/l, and the concentration of precipitating reagent is 5mol/l, dispersing agent
For PEG, the concentration of dispersing agent is 5% (w/w) of the concentration of precipitating reagent, and the feed rate of inorganic salts is 250ml/min, precipitating reagent
Feed rate be 250ml/min, high-gravity rotating bed revolving speed be 3000r/min, reaction temperature be 80 DEG C.
Comparative example 1
1) nano-ceramic particle is prepared
Reaction carries out in beaker, and inorganic salts and precipitating reagent are the same as the selection of embodiment 1 Al (NO3)3(NH4)2CO3, Al
(NO3)3Concentration is 0.3mol/l, (NH4)2CO3Concentration is 2mol/l, and dispersing agent PEG2000, the concentration of dispersing agent is precipitating reagent
Concentration 2% (w/w), (NH into round-bottomed flask4)2CO3Solution instills Al (NO dropwise3)3Solution controls (NH4)2CO3With
Al(NO3)3Molar ratio be 2.5：1, reaction temperature is 0 DEG C, stirring rate 2500r/min.Remaining post-processing and calcination condition with
Embodiment 1 is identical, obtains aluminium oxide nano ceramic particle.
2) ceramics polymer composite diaphragm is prepared
Condition and the process for preparing ceramics polymer composite diaphragm are same as Example 1.
A in Fig. 7 is scanning (SEM) photo of nano-ceramic particle made from comparative example 1.It can be seen that nano ceramics
Though particle has certain consecutive structure, there are agglomerations, cannot disperse well.
Ceramics polymer composite membrane prepared by comparative example 1 is connect with contact angle measurement measurement lithium-ion battery electrolytes
Feeler, a in Fig. 8 are contact angle photo of the electrolyte to the ceramics polymer composite membrane of comparative example 1, and contact angle is 13 °.
The ceramics polymer composite membrane of comparative example 1 is put into vacuum oven, is heated 30 minutes at different temperatures, tool
Body result is as shown in a, b, c in Fig. 9.As can be seen that the ceramics polymer of comparative example 1 is compound after heating 30min at 150 DEG C
Film shrinking percentage is 6%, and after heating 30min at 160 DEG C, the ceramics polymer composite membrane shrinking percentage of comparative example 1 is 15%.Work as temperature
After degree slightly improves, the shrinking percentage of comparative example 1 is greatly increased, and is compared shrinking percentage under the conditions of same as Example 1 and is increased by 50%, no
Adapt to higher temperature.
Comparative example 2
1) nano-ceramic particle is prepared
Firstly, presoma is prepared in high-gravity rotating bed using coprecipitation；Wherein, inorganic salts select Al
(NO3)3, concentration 0.15mol/l, precipitating reagent selection (NH4)2CO3, concentration 1mol/l, dispersing agent PEG2000, dispersing agent
Concentration be precipitating reagent concentration 2% (w/w), the feed rates of inorganic salts is 160ml/min, and the feed rate of precipitating reagent is
60ml/min, high-gravity rotating bed revolving speed 2500r/min, reaction temperature are 0 DEG C.Remaining post-processing and calcination condition and implementation
Example 1 is identical, obtains nano-ceramic particle.
2) ceramics polymer composite diaphragm is prepared
Condition and the process for preparing ceramics polymer composite diaphragm are same as Example 1.
B in Fig. 7 is scanning (SEM) photo of the nano-ceramic particle of comparative example 2.Therefrom it can be seen that comparative example 2
Nano-ceramic particle is all block structure, does not occur consecutive structure.
Ceramics polymer composite membrane prepared by comparative example 2 is connect with contact angle measurement measurement lithium-ion battery electrolytes
Feeler, the b in Fig. 8 are contact angle photo of the electrolyte to the ceramics polymer composite membrane of comparative example 2, and contact angle is 22 °.
The ceramics polymer composite membrane of comparative example 2 is put into vacuum oven, is heated 30 minutes at different temperatures, tool
Body result is as shown in d, e, f in Fig. 9.As can be seen that the ceramics polymer of comparative example 2 is compound after heating 30min at 150 DEG C
Film shrinking percentage is 7%, and after heating 30min at 160 DEG C, the ceramics polymer composite membrane shrinking percentage of comparative example 2 is 18%.
Comparative example 3
1) nano-ceramic particle is prepared
The preparation condition and process of nano-ceramic particle are same as Example 1.
2) ceramics polymer composite diaphragm is prepared
The mass ratio of nano-ceramic particle powder and binder Kynoar is 0.5:1, binder Kynoar and
The ratio of solvent acetone is 0.5g：30ml.Remaining film condition and process are same as Example 1.
Ceramics polymer composite membrane prepared by comparative example 3 is connect with contact angle measurement measurement lithium-ion battery electrolytes
Feeler, the c in Fig. 8 are contact angle photo of the electrolyte to the ceramics polymer composite membrane of comparative example 3, and contact angle is 6 °.
The ceramics polymer composite membrane of comparative example 3 is put into vacuum oven, is heated 30 minutes at different temperatures, tool
Body result is as shown in g, h, i in Fig. 9.As can be seen that the ceramics polymer of comparative example 3 is compound after heating 30min at 150 DEG C
Film shrinking percentage is 10%, and after heating 30min at 160 DEG C, the ceramics polymer composite membrane shrinking percentage of comparative example 3 is 28%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (15)
1. a kind of preparation method of ceramics polymer composite diaphragm, which is characterized in that include the following steps：
1) nano-ceramic particle is prepared
Firstly, preparing presoma in high-gravity rotating bed using coprecipitation；Wherein, the concentration of inorganic salts is 0.2-5mol/
The concentration of l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the mass concentration of dispersing agent is the 1- of the mass concentration of precipitating reagent
10%, the feed rate of inorganic salts is 10-500ml/min, and the feed rate of precipitating reagent is 10-500ml/min, hypergravity rotation
The revolving speed of bed is 500-3000r/min, and reaction temperature is -20 DEG C -80 DEG C；
Secondly, presoma is carried out decompression suction filtration, it is dried in vacuo 12-48 hours, grinds under the conditions of 40-80 DEG C after filtering object washing
Honed sieve is calcined 1-10 hours under the conditions of 500-1500 DEG C, and it is 1-5 DEG C/h that heating rate is controlled in calcining, obtains nanometer pottery
Porcelain particle；
Wherein, series connection forms consecutive structure between the nano-ceramic particle；
2) ceramic film slurry is prepared
Binder is added in solvent and is dissolved, is later added thereto nano-ceramic particle made from step 1), ball milling 2-
10 hours, obtain ceramic film slurry；
3) ceramics polymer composite diaphragm is prepared
Ceramics film slurry made from step 2) is covered on basilar memebrane, ceramics polymer composite diaphragm is obtained,
The material of the basilar memebrane is polymer material.
2. a kind of preparation method of ceramics polymer composite diaphragm according to claim 1, which is characterized in that step 1)
In, nano-ceramic particle obtained is inorganic oxide, in silica, aluminum oxide, titanium dioxide, zirconium dioxide
One or more kinds of mixtures.
3. a kind of preparation method of ceramics polymer composite diaphragm according to claim 1, which is characterized in that step 1)
In, the concentration of inorganic salts is 0.2-2mol/l, and the concentration of precipitating reagent is 1-5mol/l, and the quality of dispersing agent PEG, dispersing agent are dense
Degree is the 1-5% of precipitating reagent mass concentration, and the feed rate of inorganic salts is 10-50ml/min, and the feed rate of precipitating reagent is 50-
100ml/min, high-gravity rotating bed revolving speed are 1500-2500r/min, and reaction temperature is 0 DEG C -50 DEG C.
4. a kind of preparation method of ceramics polymer composite diaphragm according to claim 1, which is characterized in that step 2)
In, the binder is Kynoar and/or acrylic acid；The solvent is selected from acetone, N,N-dimethylformamide, dimethyl
One or more kinds of mixtures of acetamide.
5. a kind of preparation method of ceramics polymer composite diaphragm according to claim 1, which is characterized in that step 2)
In, the mass ratio of the nano-ceramic particle and binder is 1-2：1, the ratio of the binder and solvent is 1g/30ml-
2g/30ml。
6. a kind of preparation method of ceramics polymer composite diaphragm according to claim 1, which is characterized in that step 3)
In, the polymer material is polyethylene, polypropylene, Kynoar or polyvinyl alcohol.
7. the ceramics polymer composite diaphragm being prepared by any method of claim 1-6, which is characterized in that described
Ceramics polymer composite diaphragm includes：The ceramic coating of basement membrane layer and basement membrane layer two sides；
The material of the basement membrane layer is polymer material；
The ceramic coating is that nano-ceramic particle is bonded to basement membrane layer surface to obtain；
In the ceramic coating, series connection forms consecutive structure between nano-ceramic particle, and hollow reticular structure is presented in ceramic coating.
8. ceramics polymer composite diaphragm according to claim 7, which is characterized in that the nano-ceramic particle be according to
Following steps are prepared：
Firstly, preparing presoma in high-gravity rotating bed using coprecipitation；Wherein, the concentration of inorganic salts is 0.2-5mol/
The concentration of l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the mass concentration of dispersing agent is the 1- of the mass concentration of precipitating reagent
10%, the feed rate of inorganic salts is 10-500ml/min, and the feed rate of precipitating reagent is 10-500ml/min, hypergravity rotation
The revolving speed of bed is 500-3000r/min, and reaction temperature is -20 DEG C -80 DEG C；
Secondly, presoma is carried out decompression suction filtration, it is dried in vacuo 12-48 hours, grinds under the conditions of 40-80 DEG C after filtering object washing
Honed sieve is calcined 1-10 hours under the conditions of 500-1500 DEG C, and it is 1-5 DEG C/h that heating rate is controlled in calcining, obtains nanometer pottery
Porcelain particle.
9. ceramics polymer composite diaphragm according to claim 8, which is characterized in that the concentration of inorganic salts is 0.2-
The concentration of 2mol/l, precipitating reagent are 1-5mol/l, and dispersing agent PEG, the mass concentration of dispersing agent is precipitating reagent mass concentration
1-5%, the feed rate of inorganic salts are 10-50ml/min, and the feed rate of precipitating reagent is 50-100ml/min, hypergravity rotation
The revolving speed of bed is 1500-2500r/min, and reaction temperature is 0 DEG C -50 DEG C.
10. ceramics polymer composite diaphragm according to claim 8, which is characterized in that the nano-ceramic particle is nothing
Machine oxide is selected from one or more mixtures of silica, aluminum oxide, titanium dioxide, zirconium dioxide.
11. ceramics polymer composite diaphragm according to claim 7, which is characterized in that described to glue nano-ceramic particle
Tying basement membrane layer surface is to follow the steps below：
Binder is added in solvent and is dissolved, is later added thereto nano-ceramic particle obtained, ball milling 2-10 hours,
Obtain ceramic film slurry；
Ceramic film slurry obtained is covered on basilar memebrane, ceramic coating is formed, obtains ceramics polymer composite diaphragm,
The material of the basilar memebrane is polymer material.
12. ceramics polymer composite diaphragm according to claim 11, which is characterized in that the binder is polyvinylidene fluoride
Alkene and/or acrylic acid；The solvent be selected from acetone, N,N-dimethylformamide, dimethyl acetamide one or more
Mixture.
13. ceramics polymer composite diaphragm according to claim 11, which is characterized in that the nano-ceramic particle and viscous
The mass ratio for tying agent is 1-2：1, the ratio of the binder and solvent is 1g/30ml-2g/30ml.
14. ceramics polymer composite diaphragm according to claim 11, which is characterized in that the polymer material is poly- second
Alkene, polypropylene, Kynoar or polyvinyl alcohol.
15. the application of the ceramics polymer composite diaphragm as described in claim 7-14 is any, can be used as lithium ion battery every
Film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510172322.9A CN106159157B (en) | 2015-04-13 | 2015-04-13 | A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510172322.9A CN106159157B (en) | 2015-04-13 | 2015-04-13 | A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106159157A CN106159157A (en) | 2016-11-23 |
| CN106159157B true CN106159157B (en) | 2018-11-16 |
Family
ID=57337028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510172322.9A Active CN106159157B (en) | 2015-04-13 | 2015-04-13 | A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106159157B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112151728B (en) * | 2019-06-28 | 2022-04-15 | 比亚迪股份有限公司 | Lithium ion battery composite diaphragm, preparation method thereof and lithium ion battery |
| CN110571390A (en) * | 2019-08-23 | 2019-12-13 | 华南师范大学 | Method for compositely modifying lithium-sulfur battery diaphragm by salinized graphene and carbon nano tube |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN102616839A (en) * | 2012-03-30 | 2012-08-01 | 北京化工大学 | Supergravity preparation method for mesoporous titanium dioxide |
| CN102751484A (en) * | 2012-03-02 | 2012-10-24 | 河北联合大学 | Preparation method for cobaltosic oxide electrode material having one-dimensional nanometer chain structure or spherical structure |
| CN103314063A (en) * | 2011-02-21 | 2013-09-18 | 旭化成化学株式会社 | Coating material containing organic/inorganic composite, organic/inorganic composite film and antireflection member |
-
2015
- 2015-04-13 CN CN201510172322.9A patent/CN106159157B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN103314063A (en) * | 2011-02-21 | 2013-09-18 | 旭化成化学株式会社 | Coating material containing organic/inorganic composite, organic/inorganic composite film and antireflection member |
| CN102751484A (en) * | 2012-03-02 | 2012-10-24 | 河北联合大学 | Preparation method for cobaltosic oxide electrode material having one-dimensional nanometer chain structure or spherical structure |
| CN102616839A (en) * | 2012-03-30 | 2012-08-01 | 北京化工大学 | Supergravity preparation method for mesoporous titanium dioxide |
Non-Patent Citations (1)
| Title |
|---|
| "均相共沉淀法制备纳米氧化锆复合粉体";宋云华等;《功能材料》;20111231;第42卷;摘要、实验、结果与讨论以及结论部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106159157A (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10763539B2 (en) | Inorganic solid electrolyte composite slurry, method for preparing, application and lithium-ion battery having the same | |
| CN106711461A (en) | Spherical porous silicon/carbon composite material as well as preparation method and application thereof | |
| CN108281705B (en) | Modified nano SiO2Particles, method of preparing the same, and nanofiber membrane, gel electrolyte and lithium metal battery comprising the same | |
| CN108389999A (en) | Organic and inorganic composite coated porous separation film, preparation method and its lithium ion battery | |
| CN107437603A (en) | Composite diaphragm for lithium ion battery and preparation method thereof and lithium ion battery | |
| CN102324511B (en) | Preparation method for lithium ion battery composite cathode material | |
| CA2576888A1 (en) | Electrode active material with multi-element based oxide layers and preparation method thereof | |
| CN105514328A (en) | Ceramic diaphragm for lithium ion battery and preparation method of ceramic diaphragm | |
| CN109742298A (en) | Porous ceramics diaphragm slurry and preparation method thereof, battery diaphragm and battery | |
| CN108550827A (en) | A kind of preparation method of three-dimensional porous shape silicon-carbon cathode material and application | |
| CN113130869B (en) | Negative plate and lithium ion battery | |
| CN104752702B (en) | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery | |
| CN105206777B (en) | Lithium battery diaphragm of the porous inorganic oxide containing lithium ion conduction and preparation method thereof | |
| CN103545475B (en) | Barium sulfate diaphragm of lithium ion battery and preparation method thereof | |
| CN109004212B (en) | High-rate lithium manganate positive electrode material and preparation method thereof | |
| CN108963153A (en) | A kind of lithium ion battery separator and preparation method thereof | |
| TW201351758A (en) | Isolation film of electrochemical device and manufacturing method thereof | |
| EP3439070A1 (en) | Non-porous separator and use thereof | |
| CN114335536B (en) | Plastic crystal modified positive electrode solid-state battery and preparation method thereof | |
| CN108933247A (en) | A kind of simple method and product for preparing AZO and coating 523 monocrystalline nickel-cobalt-manganternary ternary anode materials | |
| CN112864352A (en) | Pole piece and lithium ion battery | |
| CN109065875A (en) | A kind of preparation method of the tertiary cathode material of Coated powder | |
| CN106159157B (en) | A kind of preparation method of ceramics polymer composite diaphragm, the ceramics polymer composite diaphragm and its application | |
| CN113371759B (en) | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material | |
| CN106450434A (en) | High-voltage high-energy-density lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |