CN106531929A - Drying process of ceramic coated bacterial cellulose porous thin film - Google Patents
Drying process of ceramic coated bacterial cellulose porous thin film Download PDFInfo
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- CN106531929A CN106531929A CN201510584354.XA CN201510584354A CN106531929A CN 106531929 A CN106531929 A CN 106531929A CN 201510584354 A CN201510584354 A CN 201510584354A CN 106531929 A CN106531929 A CN 106531929A
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- bacterial cellulose
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B7/00—Drying solid materials or objects by processes using a combination of processes not covered by a single one of groups F26B3/00 and F26B5/00
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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 invention provides a drying process of a ceramic coated bacterial cellulose porous thin film; a water-containing ceramic coated bacterial cellulose film is dehydrated and dried, so as to obtain a ceramic coated bacterial cellulose lithium ion battery separation film with even thickness. The drying process of the ceramic coated bacterial cellulose porous thin film has the advantages of simple process and low energy consumption, and is suitable for large-scale production.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, more particularly, to a kind of drying process of the ceramic coatings Bacterial cellulose porous membrane for lithium ion battery separator.
Background technology
Barrier film is the core component of lithium ion battery, has been largely fixed the important performance indexes such as the performance of lithium ion battery, safety, service life.Novel lithium ion power battery working environment compared with conventional lithium ion battery is more complicated, needs more powerful discharge and recharge, higher safety and longer service life.Traditional lithium ion battery separator cannot meet the performance requirement of electrokinetic cell.Therefore, the key areas that high performance new type power lithium-ion membrane has become the auto industry developed countries and regions technology competition such as current American, Europe, Japan are developed.Competition situation to world's new-energy automobile is produced important impact by diaphragm of power lithium ion battery technology.
At present, in lithium rechargeable battery industry, wide variety of micro-pore septum almost all adopts microporous polyolefin film, the method mainly obtains hemicrystalline thin polymer film by melting extrusion, then which is stretched, to produce many micropores in the film, its manufacture process does not need solvent, and throughput rate is higher, and macromolecular material used is polypropylene（PP）And polyethylene（PE）One of, the most cheap membrane material of category.But this kind of microporous membrane there is also many shortcomings, such as up to 0.4 μm of the crack aperture of film, and most wide 0.04 μm, voidage is up to 40% or so.Because liquid absorption is low, the raising of lithium ionic mobility is unfavorable for the large current density of battery；Meanwhile, polypropylene ductility is poor, and surface energy is low, belongs to hard bonding plasticses, is unfavorable for the bonding with positive and negative plate, and barrier film is combined with electrode interface not closely, affects the energy density of battery；Additionally, this method equipment is complicated, cost of manufacture is higher, and also costly, the production cost of battery also accordingly rises price.Additionally, the heat-shrinkable of conventional membrane is more serious, melt temperature is relatively low（PP is about 165oC）, these features make conventional membrane meet the requirement of electrokinetic cell safety.
In order to solve the above problems, all high-performance power battery barrier film is competitively being developed with countries and regions such as U.S., days.The U.S. have developed a kind of high performance lithium ion battery barrier film based on nanofiber spining technology in 2007（Energain™）, dedicated for power lithium-ion battery.After the barrier film, the power of battery can improve 15%-30%, and service life improves 20%, and the safety of battery is greatly improved.German EVONIC companies have been developed over a High-performance diaphragm dedicated for electrokinetic cell（SEPARION®）, the safe temperature of the film is up to 210oC, percent thermal shrinkage are less than 1% (200oC, 24h), wellability is obviously improved, with outstanding heat stability and chemical stability.In on April 26th, 2013, Di Ren technical products company limited under Japanese Di Ren groups announced that company develops the aramid nano-fiber that can be mass-produced first, and the fiber has higher quality, it is possible to provide reliable heat-resisting and antioxygenic property.Using the heat-resisting meta-aramid manufactures of the proprietary Teijinconex of Di Ren companies, its size uniform, diameter are only hundreds of nanometer to the nanofiber.It is reported that, aramid nano-fiber will be applied to lithium ion battery in the form of non-woven sheet（LIBs）The manufacture of barrier film, company will carry out commercially producing for the fiber in 2014.It is introduced that, till now, the aramid nano-fiber of Di Ren companies is only produced in the lab, and the sheet material of its production can keep shape at 300 DEG C.Aramid nano-fiber high temperature resistant, sludge proof performance can strengthen the safety of lithium ion batteries for automobiles and static electric power storage, it is ensured that battery reduces the danger of fire in high power capacity, high-energy-density application, has more advantage than traditional barrier film.Aramid nano-fiber non-woven sheet can be applicable to other features of battery diaphragm to be included：Electrolyte smooth flow can be promoted with high porosity, so as to have higher electric power output and quickly-chargeable ability；Surface area is big, with nanofiber feature, and high porosity, when ionic conductivity declines, can still make the electrolyte effectively performance of holding battery under cryogenic；As non-woven sheet, compared with traditional polyolefin-based separator, make electrolyte absorption rapider, contributing to shortening makes electrolyte be poured into the time needed for battery, so as to reduce the production cost of high capacity cell.
Bacterial cellulose is by microorganism（Predominantly antibacterial）The extracellular fiber element of generation, is found in 1886 by British scientist Brown earliest.Compared with plant cellulose, bacterial fibers have many features, such as high water-holding capacity；Under static culture conditions, ability is maintained with high Young's modulus, high-tensile and splendid shape；High-crystallinity；It is ultra-fine（Nanoscale）Fibrous reticular structure；The high-altitude fixed rate of interest（>90%）；High-purity（99 more than % are celluloses）；Higher biocompatibility and good biodegradability；Physical property controllable etc. during biosynthesiss.Because Bacterial cellulose has above-mentioned premium properties at aspects such as purity, absorbency, physical and mechanical properties, people attach great importance to its applied research in every field, also have extensive commercial applications potentiality in terms of lithium ion battery separator.
However, bacterial cellulose wet-coating is processed into lithium ion battery separator to need to overcome several key technical problems：（1）The thickness of cellulosic separator should be less than 40 microns；（2）Cellulosic separator thickness is uniform；（3）Bacterial cellulose barrier film should have higher voidage.And the technique such as traditional lyophilization, supercritical drying has complex process, high cost, the shortcomings of arid cycle is long.And convection drying bacterial cellulose wet-coating barrier film then has the shortcomings that energy consumption is big, membrane porosity is little, ionic conductivity is low by the way of hot pressing.
Wang Biao et al. has carried out the research of lithium battery bacteria cellulose film gel polymer electrolyte, and they are incorporated into lithium salts organic solution in bacterial cellulose wet-coating with displacement method, are prepared for polymer gel.But the battery performance of polymeric electrolyte gels film that this method is obtained is undesirable.They are prepared for composite gel electrolyte film further through the method for the addition silica dioxide granule in bacterial cellulose gel film, it is dispersed in the hole of bacteria cellulose film yet with silica dioxide granule, the porosity of cellulose membrane can not be effectively increased, the adsorbance of electrolyte is likely to reduced on the contrary, so electrical conductivity have dropped on the contrary.Jiang Fengjing et al. is prepared for ultra-thin bacteria cellulose film barrier film using improved technique（Dry film）, however, it was found that the ultra-thin Bacterial cellulose barrier film porosity for preparing is relatively low, so as to cause the barrier film of Conductivity Ratio business low.
The problem that inventor is present for above-mentioned key technology, a kind of ceramic coatings Bacterial cellulose porous membrane for lithium ion battery separator with excellent lyophily, higher porosity and ionic conductivity, outstanding resistance to elevated temperatures is invented, with and preparation method thereof, the preparation method is simple, efficient, the characteristics of Bacterial cellulose porous membrane for preparing has ionic conductivity height, high temperature resistant, good battery performance, can be used to prepare high-performance, resistant to elevated temperatures lithium ion battery separator.
The present invention further provides a kind of drying meanss rapidly and efficiently for the ceramic coatings Bacterial cellulose porous membrane invented before inventor, with improve production efficiency, reduces production cost.
The content of the invention
For ceramic coatings Bacterial cellulose porous membrane slow drying speed, the higher problem of energy consumption, the invention provides proposing a kind of drying meanss of ceramic coatings Bacterial cellulose porous membrane rapidly and efficiently, with improve production efficiency, production cost is reduced.
The technical scheme is that：
A kind of drying process of ceramic coatings Bacterial cellulose porous membrane, it is characterised in that：Drying process includes dry, three steps of hot-pressing drying and hot air drying of colding pressing successively；
Described drying of colding pressing, it is characterised in that：Press used is that hydraulic pressure is extruded or air pressure press, and pressure is 0.1 ~ 1MPa, and temperature is room temperature, without the need for heating；
Described hot-pressing drying, it is characterised in that：Press used is hydraulic press or air pressure press, and pressure is 0.1 ~ 1MPa, and upper and lower two block pressur plate of press has heating function, and hot pressing temperature is 80 ~ 120oC；
Described hot air drying, it is characterised in that：Hot blast temperature is 80 ~ 150oC, wind speed are more than 2-12 m/s；
The drying process of described ceramic coatings Bacterial cellulose porous membrane, it is characterised in that：Three steps are connected using a conveyer belt.
According to the ceramic coatings Bacterial cellulose porous membrane that said method is obtained, porosity is more than 50%.It is very suitable for preparing lithium ion battery separator.The drying process of ceramic coatings Bacterial cellulose porous membrane of the present invention, with preparation process is simple, energy consumption is low, efficiency high, is adapted to the distinguishing feature of large-scale production.
Description of the drawings
Fig. 1 is the process chart of the drying process of ceramic coatings Bacterial cellulose porous membrane described in the invention.
Fig. 2 is the battery charging and discharging Performance comparision of the ceramic coatings bacteria cellulose film prepared by the present invention and business Celgard barrier film.It can be seen that the battery capacity of the present invention and the abundant electrical property of high magnification are significantly better than that Celgard business barrier films.
Specific embodiment
Below embodiments of the invention are elaborated.The present embodiment is implemented lower premised on technical solution of the present invention, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to protection scope of the present invention.
Embodiment 1：
First ceramic coatings bacterial cellulose film is put on conveyer belt and is sent to press of colding pressing, press top board of colding pressing moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.1 MPa is extruded, burn close time is 1 minute, and the most of hydraulic pressure contained in film is gone out thin film.During matched moulds, conveyer belt stops.Then pressing plate die sinking（Top board is moved up）, conveyer belt delivers to thin film in the middle of the pressing plate of hot press, and hot press top board moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.1 MPa is extruded, and burn close time is 10 minutes, and upper and lower platen temperature is 80oC, film hot pressing is dried.During matched moulds, conveyer belt stops.Then heating platen die sinking（Top board is moved up）, thin film delivered to hot-air blower air outlet and carries out hot air drying by conveyer belt, and wind speed is 4m/s, and it is 150 that hot blast reaches the temperature on film surface oC, drying time is 2 minutes.During hot air drying, conveyer belt stops.
The porosity of ceramic coatings bacteria cellulose film prepared by described drying process is more than 50%, and its performance on lithium ion battery is as shown in Figure 2.
Embodiment 2：
First ceramic coatings bacterial cellulose film is put on conveyer belt and is sent to press of colding pressing, press top board of colding pressing moves downward and the pressure that ceramic coatings bacterial cellulose film applies 1 MPa is extruded, burn close time is 0.5 minute, and the most of hydraulic pressure contained in film is gone out thin film.During matched moulds, conveyer belt stops.Then pressing plate die sinking（Top board is moved up）, conveyer belt delivers to thin film in the middle of the pressing plate of hot press, and hot press top board moves downward and the pressure that ceramic coatings bacterial cellulose film applies 1 MPa is extruded, and burn close time is 3 minutes, and upper and lower platen temperature is 120oC, film hot pressing is dried.During matched moulds, conveyer belt stops.Then heating platen die sinking（Top board is moved up）, thin film delivered to hot-air blower air outlet and carries out hot air drying by conveyer belt, and wind speed is 4m/s, and it is 80 that hot blast reaches the temperature on film surface oC, drying time is 1 minute.During hot air drying, conveyer belt stops.
The porosity of ceramic coatings bacteria cellulose film prepared by described drying process is more than 50%, and its performance on lithium ion battery is as shown in Figure 2.
Embodiment 3：
First ceramic coatings bacterial cellulose film is put on conveyer belt and is sent to press of colding pressing, press top board of colding pressing moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.3 MPa is extruded, burn close time is 0.2 minute, and the most of hydraulic pressure contained in film is gone out thin film.During matched moulds, conveyer belt stops.Then pressing plate die sinking（Top board is moved up）, conveyer belt delivers to thin film in the middle of the pressing plate of hot press, and hot press top board moves downward and the pressure that ceramic coatings bacterial cellulose film applies 1 MPa is extruded, and burn close time is 2 minutes, and upper and lower platen temperature is 100oC, film hot pressing is dried.During matched moulds, conveyer belt stops.Then heating platen die sinking（Top board is moved up）, thin film delivered to hot-air blower air outlet and carries out hot air drying by conveyer belt, and wind speed is 8m/s, and it is 100 that hot blast reaches the temperature on film surface oC, drying time is 0.5 minute.During hot air drying, conveyer belt stops.
The porosity of ceramic coatings bacteria cellulose film prepared by described drying process is more than 50%, and its performance on lithium ion battery is as shown in Figure 2.
Embodiment 4：
First ceramic coatings bacterial cellulose film is put on conveyer belt and is sent to press of colding pressing, press top board of colding pressing moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.8 MPa is extruded, burn close time is 0.6 minute, and the most of hydraulic pressure contained in film is gone out thin film.During matched moulds, conveyer belt stops.Then pressing plate die sinking（Top board is moved up）, conveyer belt delivers to thin film in the middle of the pressing plate of hot press, and hot press top board moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.8 MPa is extruded, and burn close time is 5 minutes, and upper and lower platen temperature is 90oC, film hot pressing is dried.During matched moulds, conveyer belt stops.Then heating platen die sinking（Top board is moved up）, thin film delivered to hot-air blower air outlet and carries out hot air drying by conveyer belt, and wind speed is 12m/s, and it is 120 that hot blast reaches the temperature on film surface oC, drying time is 1 minute.During hot air drying, conveyer belt stops.
The porosity of ceramic coatings bacteria cellulose film prepared by described drying process is more than 50%, and its performance on lithium ion battery is as shown in Figure 2.
Embodiment 5：
First ceramic coatings bacterial cellulose film is put on conveyer belt and is sent to press of colding pressing, press top board of colding pressing moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.3MPa is extruded, burn close time is 1 minute, and the most of hydraulic pressure contained in film is gone out thin film.During matched moulds, conveyer belt stops.Then pressing plate die sinking（Top board is moved up）, conveyer belt delivers to thin film in the middle of the pressing plate of hot press, and hot press top board moves downward and the pressure that ceramic coatings bacterial cellulose film applies 0.3 MPa is extruded, and burn close time is 1 minute, and upper and lower platen temperature is 120oC, film hot pressing is dried.During matched moulds, conveyer belt stops.Then heating platen die sinking（Top board is moved up）, thin film delivered to hot-air blower air outlet and carries out hot air drying by conveyer belt, and wind speed is 6 m/s, and it is 120 that hot blast reaches the temperature on film surface oC, drying time is 1 minute.During hot air drying, conveyer belt stops.
The porosity of ceramic coatings bacteria cellulose film prepared by described drying process is more than 50%, and its performance on lithium ion battery is as shown in Figure 2.
Claims (5)
1. a kind of drying process of ceramic coatings Bacterial cellulose porous membrane, it is characterised in that：Drying process includes dry, three steps of hot-pressing drying and hot air drying of colding pressing successively.
2. drying of colding pressing according to claim 1, it is characterised in that：Press used is that hydraulic pressure is extruded or air pressure press, and pressure is 0.1 ~ 1MPa, and temperature is room temperature, without the need for heating.
3. hot-pressing drying according to claim 1, it is characterised in that：Press used is hydraulic press or air pressure press, and pressure is 0.1 ~ 1MPa, and upper and lower two block pressur plate of press has heating function, and hot pressing temperature is 80 ~ 120oC。
4. hot air drying according to claim 1, it is characterised in that：Hot blast temperature is 80 ~ 150oC, wind speed are more than 4m/s.
5. the drying process of a kind of ceramic coatings Bacterial cellulose porous membrane according to claim 1, it is characterised in that：Three steps are connected using a conveyer belt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357352A (en) * | 2019-07-09 | 2019-10-22 | 容健美 | A kind of multistage printing and dyeing wastewater decolorizing process technique |
| CN110464876A (en) * | 2019-08-30 | 2019-11-19 | 河南亚都实业有限公司 | A kind of growth factor-loaded bacteria cellulose/bioceramic composite membrane |
| CN113270686A (en) * | 2021-05-25 | 2021-08-17 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
| CN114094278A (en) * | 2021-10-20 | 2022-02-25 | 中材锂膜有限公司 | Novel lithium ion battery diaphragm drying device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1832985A (en) * | 2003-07-31 | 2006-09-13 | 国立大学法人京都大学 | Fiber-reinforced composite material, manufacturing method therefor, and wiring base |
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
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2015
- 2015-09-15 CN CN201510584354.XA patent/CN106531929A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832985A (en) * | 2003-07-31 | 2006-09-13 | 国立大学法人京都大学 | Fiber-reinforced composite material, manufacturing method therefor, and wiring base |
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110357352A (en) * | 2019-07-09 | 2019-10-22 | 容健美 | A kind of multistage printing and dyeing wastewater decolorizing process technique |
| CN110464876A (en) * | 2019-08-30 | 2019-11-19 | 河南亚都实业有限公司 | A kind of growth factor-loaded bacteria cellulose/bioceramic composite membrane |
| CN110464876B (en) * | 2019-08-30 | 2022-03-29 | 东营凤起生物科技发展有限公司 | Growth factor-loaded bacterial cellulose/biological ceramic composite membrane |
| CN113270686A (en) * | 2021-05-25 | 2021-08-17 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
| CN113270686B (en) * | 2021-05-25 | 2023-01-31 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
| CN114094278A (en) * | 2021-10-20 | 2022-02-25 | 中材锂膜有限公司 | Novel lithium ion battery diaphragm drying device |
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