CN110098367A - A kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm and preparation method thereof - Google Patents
A kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm and preparation method thereof Download PDFInfo
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- CN110098367A CN110098367A CN201910466429.2A CN201910466429A CN110098367A CN 110098367 A CN110098367 A CN 110098367A CN 201910466429 A CN201910466429 A CN 201910466429A CN 110098367 A CN110098367 A CN 110098367A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm and preparation method thereof, belongs to lithium-sulfur cell technical field.The modified diaphragm is the compound for forming carbon nanotube and titanium dioxide nanoplate layer, is coated to and obtains on membrane surface.Since titanium dioxide nanoplate layer has bigger specific surface area, modified diaphragm prepared by the present invention is used, the battery high rate performance and cycle performance of lithium-sulfur cell are improved significantly.The results showed that in the voltage range of 1.5-3V, carrying out charge-discharge test at 30 DEG C of constant temperature with the current density of 1C, circulation 100 times, certain discharge capacity is still kept, while under 0.2C multiplying power, reaches 1249mAh g using the battery first discharge specific capacity of modified diaphragm‑1.The composite coating has production cost low simultaneously, and high-volume industrial production may be implemented in the advantages such as easy to operate.
Description
Technical field
The invention belongs to lithium-sulfur cell technical fields, and in particular to a kind of carbon nano-tube/titanic oxide nano lamella is compound
Object modified diaphragm and preparation method thereof.
Background technique
With the continuous upgrading of portable electronic device and new-energy automobile, develop environmental protection, low cost, high-energy density,
The energy storage device of recyclable charge and discharge obtains the extensive concern of industry.Wherein lithium-sulfur cell theoretical capacity with higher
(1672mA g-1) and theoretical energy density (2600Wh kg-1), it is expected to become the main research side of next-generation high energy-storage system
To.However, there are some problems, such as " the shuttle effect " of battery intermediate product polysulfide, sulfur materials itself for lithium-sulfur cell
The volume expansion of sulphur in poor electric conductivity and reaction process.The development and industrialization of these problems limitation lithium-sulfur cell.Lithium
Sulphur battery can generate a large amount of polysulfide during discharge, these polysulfides dissolve in the electrolytic solution, spread from cathode
To anode, irreversible S is formedn 2-, constantly it is lost so as to cause active material, anodic passivity, kinetics reduces.Therefore,
" shuttle effect " is the key reason of lithium-sulfur cell performance.
In order to inhibit " the shuttle effect " in lithium-sulfur cell, people use many different strategies, are included in sulphur anode
Upper addition basis material, modification diaphragm, addition middle layer etc..In these methods, modified diaphragm can be adsorbed effectively
Polysulfide, therefore be always the emphasis studied to diagram modification.Show that modified diaphragm should have by previous research experience
Standby property below: good electric conductivity, continuous whole membrane structure, excellent electrolyte wettability and polysulfide absorption
Property.Therefore, Multimetal oxide, transient metal sulfide, metal organic framework and polymer be all used as it is modified every
The material of film.Titanium dioxide and polysulfide form S-Ti-O key, to reach fixed polysulfide by acting between electronics
Effect.Therefore it has been reported that about titanium dioxide nano-particle, mesoporous TiO 2 and titania nanotube and carbon materials
Material is combined into composite material and is modified to diaphragm, and is applied in lithium-sulfur cell, however, about titanium dioxide nanoplate is utilized
The research or blank of the modified lithium-sulfur cell diaphragm of layer material.
Summary of the invention
For above-mentioned the technical issues of occurring, the object of the present invention is to provide a kind of carbon nano-tube/titanic oxide nano pieces
Layer compound modified diaphragm and preparation method thereof, by the way that the modified diaphragm is applied on lithium-sulfur cell, the battery of lithium-sulfur cell
High rate performance and cycle performance are improved significantly.
To achieve the above object, the present invention adopts the following technical solutions:
Present invention firstly provides a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm, the modifications
Diaphragm is the compound for forming carbon nanotube and titanium dioxide nanoplate layer, is coated to and obtains on membrane surface.
Preferably, the diaphragm is polyethylene diagrams, polypropylene diaphragm or polyethylene and polypropylene multilayer separator.
Preferably, the compound that the carbon nanotube and titanium dioxide nanoplate layer are formed with a thickness of 8-12 μm.
Preferably, the preparation method for the compound that the carbon nanotube and titanium dioxide nanoplate layer are formed, comprising:
Carbon nanotube, titanium dioxide nanoplate layer, surfactant and binder are dissolved in solvent, by ultrasonic disperse, obtain carbon
The compound that nanotube and titanium dioxide nanoplate layer are formed.
Preferably, the surfactant is polyvinylpyrrolidone.
Preferably, the binder is sodium carboxymethylcellulose.
Preferably, the carbon nanotube and titanium dioxide nanoplate layer mass ratio are (3-9): (1-2).
Preferably, the carbon nanotube and titanium dioxide nanoplate layer mass ratio are 4:1.
Preferably, the titanium dioxide nanoplate layer is having a size of 100-150nm, with a thickness of 10nm-30nm, specific surface
Product is greater than 400m2/g。
The present invention also provides a kind of preparation method of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm, packets
It includes:
Step 1: carbon nanotube, titanium dioxide nanoplate layer, surfactant and binder are dissolved in solvent, are passed through
Ultrasonic disperse obtains the compound of carbon nanotube and the formation of titanium dioxide nanoplate layer；
Step 2: in the composite coated to diaphragm that step 1 is obtained, carbon nanotube/bis- are obtained after dry cut out
TiOx nano lamella compound modified diaphragm.
The principle of the present invention
The present invention utilizes carbon nanotube and nano titania aiming at the problem that improving lithium-sulfur cell capacity and cycle performance
Lamella composite modification mainly inhibits shuttle effect in terms of three, specifically:
First: carbon nanotube has good electric conductivity, is conducive to the transmission of electronics, forms net after one-dimentional structure film forming
Shape structure is conducive to improve the continuity and mechanicalness of film, while conductive carbon nanotube can serve as upper layer collector, have
There is biggish specific surface area that can adsorb polysulfide by physical action.
Second: titanium dioxide nanoplate layer has bigger specific surface area than titania nanoparticles, provides more mistake
Site is chemically reacted, the fixed polysulfide of chemical bonding S-Ti-O is passed through.Its layer structure is conducive to be dispersed in carbon nanometer simultaneously
In the reticular structure that pipe is formed, further physics prevents the shuttle of polysulfide.
Third: the carbon nano-tube/titanic oxide nano lamella composite modification diaphragm of optimization has excellent electrolyte
Wetability, to improve interface compatibility, shorten the electrolyte filling time, promote lithium ion mobility.
Beneficial effects of the present invention
The present invention provides a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm and preparation method thereof, should
Modified diaphragm is the compound for forming carbon nanotube and titanium dioxide nanoplate layer, is coated to and obtains on membrane surface.By
There is bigger specific surface area than titania nanoparticles in titanium dioxide nanoplate layer, while more having than mesoporous TiO 2
Conducive to the continuity and integrality of modified film, therefore use modified diaphragm prepared by the present invention, the battery multiplying power of lithium-sulfur cell
Performance and cycle performance are improved significantly.The results showed that at 30 DEG C of constant temperature, in the voltage range of 1.5-3V,
Charge-discharge test is carried out with the current density of 1C, recycles 100 times, still keeps certain discharge capacity.Simultaneously under 0.2C multiplying power, make
Reach 1249mAh g with the battery first discharge specific capacity of modified diaphragm-1.The composite coating has production cost low simultaneously, behaviour
Make the advantages such as simple, high-volume industrial production may be implemented.
Detailed description of the invention
Fig. 1 is the scanning on carbon nano-tube/titanic oxide nano lamella compound modified diaphragm surface obtained by embodiment 1
The photo (figure b) of electron micrograph (figure a) and diaphragm.
Fig. 2 is the electrolyte contacts angle test chart of embodiment 1 (figure b) with comparative example 1 (figure a).
Fig. 3 is Li2S6Solution and the Li that titanium dioxide nanoplate layer is added2S6Photo after solution stand 24 hours.
Fig. 4 is the x-ray photoelectron spectroscopy comparison diagram of titanium elements in 1 pair of embodiment circulation front and back diaphragm.
Fig. 5 is embodiment 1, embodiment 2, embodiment 3, and the improvement diaphragm that pure PP and comparative example 2 obtain is applied in lithium sulphur electricity
Specific discharge capacity in pond recycles figure.
Specific embodiment
Present invention firstly provides a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm, the modifications
Diaphragm is the compound for forming carbon nanotube and titanium dioxide nanoplate layer, is coated to and obtains on membrane surface.
According to the present invention, the diaphragm is not particularly limited, using diaphragm well known in the art, preferably polyethylene
Diaphragm, polypropylene diaphragm or polyethylene and polypropylene multilayer separator.
According to the present invention, the thickness of the compound of the carbon nanotube and the formation of titanium dioxide nanoplate layer is preferably 8-
12μm。
According to the present invention, the preparation method of the compound of the carbon nanotube and the formation of titanium dioxide nanoplate layer is excellent
Choosing includes: that carbon nanotube, titanium dioxide nanoplate layer, surfactant and binder are dissolved in solvent, by ultrasonic disperse,
The excusing from death jitter time is preferably 1-2 hours, obtains the compound of carbon nanotube and the formation of titanium dioxide nanoplate layer.Institute
The surfactant stated is preferably polyvinylpyrrolidone, and binder is preferably sodium carboxymethylcellulose, and solvent is preferably isopropyl
Alcohol.
According to the present invention, the carbon nanotube and titanium dioxide nanoplate layer mass ratio are preferably (3-9): (1-2), more
Preferably 4:1, the additional amount of the surfactant are preferably carbon nanotube and titanium dioxide nanoplate layer gross mass
5%, the additional amount of binder is preferably the 5% of carbon nanotube and titanium dioxide nanoplate layer gross mass.
According to the present invention, the titanium dioxide nanoplate layer compares table having a size of 100-150nm with a thickness of 10nm-30nm
Area is greater than 400m2/ g has excellent polysulfide adsorptivity.The titanium dioxide nanoplate layer use it is well known that
Preparation method preparation, be not particularly limited, it is preferred to use obtained by chemical method stripping nano particle.
According to the present invention, the source of the carbon nanotube be it is commercially available, be not particularly limited.
The present invention also provides a kind of preparation method of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm, packets
It includes:
Step 1: carbon nanotube, titanium dioxide nanoplate layer, surfactant and binder are dissolved in solvent, are passed through
Ultrasonic disperse obtains the compound of carbon nanotube and the formation of titanium dioxide nanoplate layer；
Step 2: in the composite coated to diaphragm that step 1 is obtained, carbon nanotube/bis- are obtained after dry cut out
TiOx nano lamella compound modified diaphragm.
According to the present invention, the coating preferably uses vacuum filtration mode uniformly to filter compound on diaphragm.
According to the present invention, the above-mentioned carbon nano-tube/titanic oxide nano lamella compound modified diaphragm being prepared is answered
It uses in lithium-sulfur cell, steps are as follows:
(1) it prepares positive electrode: elemental sulfur, acetylene black and binder 7:2:1 in mass ratio being prepared into slurry, then applied
The pole piece that diameter is 12mm is cut on cloth to aluminium foil after vacuum dried drying；
(2) button cell is assembled into glove box for testing according to the sequence of sulphur anode, modified diaphragm, metal lithium sheet
Chemical property.
The result shows that: at 30 DEG C of constant temperature, in the voltage range of 1.5-3V, charge and discharge electrical measurement is carried out with the current density of 1C
Examination recycles 100 times, still keeps certain discharge capacity.Simultaneously under 0.2C multiplying power, discharged for the first time ratio using the battery of modified diaphragm
Capacity reaches 1249mAh g-1。
Further detailed description is done to invention combined with specific embodiments below, the raw material being related in embodiment is quotient
Purchase obtains.
Embodiment 1
(1), lamella titanium dioxide nanoplate layer is synthesized
A) 0.1g anatase titania nanoparticle is put into mortar, fine grinding prevents from assembling.
B) titanium dioxide nano-particle after grinding is added in 10ml 10M NaOH aqueous solution and is stirred 30 minutes.
C) add 8g tetrabutylammonium hydroxide in the above solution, stir 30 minutes.
D) it is transferred in the above solution in the reaction kettle of 100ml, 130 DEG C of baking ovens heat 24 hours.
E) solution is centrifuged after cooling, respectively deionization washing, alcohol washes.
F) 80 DEG C of dry collections, obtained titanium dioxide lamella size are 100nm, and with a thickness of 10nm, specific surface area is about
400m2/g。
(2), carbon nano-tube/titanic oxide nano lamella compound modified diaphragm is prepared
A) carbon nanotube and the titanium dioxide nanoplate layer of synthesis are weighed according to mass ratio 4:1.
B) in mass ratio by carbon nanotube, titanium dioxide nanoplate layer, polyvinylpyrrolidone and sodium carboxymethylcellulose
4:1:0.25:0.25 is dispersed in isopropanol, is allowed to the 1h that is uniformly dispersed in a solvent using ultrasonic vibration, is obtained composite diffusion
Liquid；
C) homogeneous dispersion is filtered onto the PP diaphragm of business using vacuum filtration mode, is prepared after dry cut out
MWCNTs@TiO out2Modified lithium-sulfur cell diaphragm.The carbon nanotube and titanium dioxide nanoplate layer form compound
Object with a thickness of 10 μm.
The above-mentioned carbon nano-tube/titanic oxide nano lamella compound modified diaphragm being prepared is applied to lithium-sulfur cell
In, steps are as follows:
By elemental sulfur, acetylene black and binder 7:2:1 in mass ratio are prepared into slurry, are then applied on aluminium foil through vacuum
The pole piece that diameter is 12mm is cut into after dry drying.
According to sulphur anode, above-mentioned modified diaphragm, metal lithium sheet sequence in glove box assembled formation button cell be used for
Test chemical property.
The results showed that in the voltage range of 1.5-3V, carrying out charge and discharge at 30 DEG C of constant temperature with the current density of 1C
Electrical testing recycles 100 times.It recycles 100 times and still maintains certain discharge capacity.Simultaneously under 0.2C multiplying power, using carbon nanotube/
The battery first discharge specific capacity of titanium dioxide nanoplate layer diaphragm reaches 1249mAh/g.The results are shown in Table 1.
Fig. 1 is the scanning on carbon nano-tube/titanic oxide nano lamella compound modified diaphragm surface obtained by embodiment 1
The photo (figure b) of electron micrograph (figure a) and diaphragm.It can be clearly seen that from figure, titanium dioxide nanoplate and carbon
Nanotube is good to be dispersed on diaphragm, and modified diaphragm has good continuity, and decorative layer adhesive force is preferable.
Fig. 2 is the electrolyte contacts angle test chart of embodiment 1 (figure b) with comparative example 1 (figure a).It can from test result
Out, titanium dioxide nanoplate layer/carbon nanotube improvement diaphragm contact angle is 9.8 °, the contact of simple carbon nanotube improvement diaphragm
Angle is 157.0 °.Illustrate that titanium dioxide nanoplate layer/carbon nano tube modified layer can accelerate the infiltration of electrolyte, is conducive to improve
Interface compatibility, accelerates the migration of lithium ion, to improve the charge-discharge performance of lithium-sulfur cell.
Fig. 3 is Li2S6Solution and the Li that titanium dioxide nanoplate layer is added2S6Photo after solution stand 24 hours, in figure
As can be seen that a figure is Li2S6Solution (buff), b figure are the Li in same concentrations2S6Titanium dioxide nanoplate is added in solution
Layer, (faint yellow) comparison of photo after static 24 hours, illustrates titanium dioxide nanoplate layer to Li2S6There is suction-operated.
Fig. 4 is the x-ray photoelectron spectroscopy comparison diagram of titanium elements in 1 pair of embodiment circulation front and back diaphragm.The structure from figure
It was determined that titanium elements can be with sulphur bonding, thus may determine that titanium dioxide nanoplate layer can be acted on by chemical bonding
Fixed polysulfide.
Embodiment 2
The preparation method is the same as that of Example 1, the difference is that the mass ratio of carbon nanotube and titanium dioxide nanoplate layer is 9:
1。
Modified diaphragm prepared by embodiment 2 is applied in lithium-sulfur cell and is tested, the results are shown in Table 1.
Embodiment 3
The preparation method is the same as that of Example 1, the difference is that the mass ratio of carbon nanotube and titanium dioxide nanoplate layer is 3:
2。
Modified diaphragm prepared by embodiment 3 is applied in lithium-sulfur cell and is tested, the results are shown in Table 1.
1 single carbon nanotube modified diaphragm of comparative example
Carbon nanotube, polyvinylpyrrolidone and sodium carboxymethylcellulose are dispersed according to mass ratio 6:0.3:0.3 different
In propyl alcohol, the 1h that is uniformly dispersed in a solvent is allowed to using ultrasonic vibration, obtains dispersion liquid.
C) above-mentioned homogeneous dispersion is filtered onto the PP diaphragm of business using vacuum filtration mode, after dry cut out
Prepare the modified lithium-sulfur cell diaphragm of MWCNTs.
Modified diaphragm prepared by comparative example 1 is applied in lithium-sulfur cell and is tested, the results are shown in Table 1.
Respectively with above-described embodiment 1, embodiment 2, embodiment 3, the modification for lithium-sulfur cell prepared by comparative example 1 every
Film, lithium piece are 2032 formula button electricity of cathode preparation, and in the voltage range of 1.5-3V, carry out charge and discharge with the current density of 0.2C
Test recycles 200 times, and the results are shown in Table 1.
Table 1
Fig. 5 is embodiment 1, embodiment 2, embodiment 3, and the improvement diaphragm that pure PP and comparative example 2 obtain is applied in lithium sulphur electricity
Specific discharge capacity in pond recycles figure.It can be seen from the figure that when the titanium dioxide nanoplate that mass ratio is 1:4 in embodiment 1
The diaphragm effect of layer/carbon nanotube improvement is best, and wherein mass ratio is the titanium dioxide nanoplate layer carbon nanotube of 1:9 and 2:3
The diaphragm effect of improvement is also preferable, is all better than unmodified PP diaphragm.
Claims (10)
1. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm, which is characterized in that the modified diaphragm is
Compound that carbon nanotube and titanium dioxide nanoplate layer are formed is coated to and obtains on membrane surface.
2. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 1, feature exist
In the diaphragm is polyethylene diagrams, polypropylene diaphragm or polyethylene and polypropylene multilayer separator.
3. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 1, the carbon
The compound that nanotube and titanium dioxide nanoplate layer are formed with a thickness of 8-12 μm.
4. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 1, the carbon
The preparation method for the compound that nanotube and titanium dioxide nanoplate layer are formed, comprising: by carbon nanotube, titanium dioxide nanoplate
Layer, surfactant and binder are dissolved in solvent, by ultrasonic disperse, obtain carbon nanotube and titanium dioxide nanoplate layer shape
At compound.
5. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 4, the table
Face activating agent is polyvinylpyrrolidone.
6. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 4, described is viscous
Knot agent is sodium carboxymethylcellulose.
7. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 4, the carbon
Nanotube and titanium dioxide nanoplate layer mass ratio are (3-9): (1-2).
8. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 7, the carbon
Nanotube and titanium dioxide nanoplate layer mass ratio are 4:1.
9. a kind of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 4, described two
TiOx nano lamella size is 100-150nm, and with a thickness of 10nm-30nm, specific surface area is greater than 400m2/g。
10. a kind of preparation side of carbon nano-tube/titanic oxide nano lamella compound modified diaphragm according to claim 1
Method characterized by comprising
Step 1: carbon nanotube, titanium dioxide nanoplate layer, surfactant and binder are dissolved in solvent, by ultrasound
Dispersion obtains the compound of carbon nanotube and the formation of titanium dioxide nanoplate layer；
Step 2: in the composite coated to diaphragm that step 1 is obtained, carbon nanotube/titanium dioxide is obtained after dry cut out
Titanium nanoscale twins compound modified diaphragm.
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| CN111584800A (en) * | 2020-01-15 | 2020-08-25 | 武汉理工大学 | Oxygen-deficient titanium dioxide nanosheet modified lithium ion battery diaphragm and preparation method and application thereof |
| CN112332025A (en) * | 2020-11-10 | 2021-02-05 | 南京工业大学 | Diaphragm for lithium-sulfur battery and preparation method thereof |
| CN112952286A (en) * | 2021-02-02 | 2021-06-11 | 同济大学 | Composite diaphragm, preparation method and application |
| CN114976491A (en) * | 2022-06-16 | 2022-08-30 | 江苏厚生新能源科技有限公司 | High-heat-resistance battery diaphragm based on titanium dioxide coaxial tube and preparation method thereof |
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| CN112952286A (en) * | 2021-02-02 | 2021-06-11 | 同济大学 | Composite diaphragm, preparation method and application |
| CN114976491A (en) * | 2022-06-16 | 2022-08-30 | 江苏厚生新能源科技有限公司 | High-heat-resistance battery diaphragm based on titanium dioxide coaxial tube and preparation method thereof |
| CN114976491B (en) * | 2022-06-16 | 2023-09-01 | 江苏厚生新能源科技有限公司 | High heat-resistant battery diaphragm based on titanium dioxide coaxial tube and preparation method thereof |
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