CN111477822A - Graphene battery diaphragm and preparation method thereof - Google Patents
Graphene battery diaphragm and preparation method thereof Download PDFInfo
- Publication number
- CN111477822A CN111477822A CN202010277795.6A CN202010277795A CN111477822A CN 111477822 A CN111477822 A CN 111477822A CN 202010277795 A CN202010277795 A CN 202010277795A CN 111477822 A CN111477822 A CN 111477822A
- Authority
- CN
- China
- Prior art keywords
- graphene
- polyvinylidene fluoride
- nanofiber membrane
- roller
- battery diaphragm
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- H01M50/411—Organic material
-
- 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
- H01M50/44—Fibrous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
-
- 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 graphene battery diaphragm and a preparation method thereof, wherein the graphene battery diaphragm comprises an upper polyvinylidene fluoride-based polymer nanofiber membrane and a lower polyvinylidene fluoride-based polymer nanofiber membrane, and a middle polyvinylidene fluoride-based graphene nanofiber membrane; the graphene battery diaphragm is prepared by a technology of preparing a nanofiber diaphragm by an electrostatic spinning method, and the prepared graphene battery diaphragm comprises the following components in parts by weight: small fiber diameter, large specific surface area, high electrolyte adsorption rate and good membrane wettability; according to the preparation method, the graphene battery diaphragm compounding equipment is used for compounding, the polyvinylidene fluoride-based graphene nanofiber membrane is pressurized by the graphene battery diaphragm compounding equipment through the extrusion rollers and the pressure bearing plates, so that the fibers are tightly connected, the heating roller is used for heating and melting, the upper pressing roller and the lower pressing roller are extruded and compounded, and the composite material is cooled and shaped when passing through the cooling roller, so that the wettability of the diaphragm is further improved, and the quality of the graphene battery diaphragm is high.
Description
Technical Field
The invention relates to the field of production processes of battery diaphragms of lithium batteries, in particular to a graphene battery diaphragm and a preparation method thereof.
Background
The diaphragm of the lithium battery is used for separating the positive electrode and the negative electrode of the battery, is an important component of the battery, enables electrons in the battery not to freely pass through, enables electrolyte ions-lithium ions to freely flow at the positive electrode and the negative electrode, maintains the normal energy exchange of the battery, prevents the short circuit of the battery and is indispensable to work.
At present, the diaphragms used by lithium batteries are mainly polyolefin polymer membranes produced by a biaxial tension method, the materials are mainly Polyethylene (PE) and polypropylene (PP), the structures of the diaphragms are single-layer or multi-layer, dry methods and wet methods are adopted in the process, organic or inorganic substances are plated on the diaphragms, the diaphragms have the defects, mainly the porosity of the diaphragms is low and is only about 40%, the adsorption capacity of electrolytes is low and is lower than 150%, the porosity distribution is wide, and the safety is poor. The migration of lithium ions is limited, and the charging and discharging of large current are not facilitated.
Therefore, the patent with the application number of CN201610177850.8 discloses a battery diaphragm, a preparation method thereof and a lithium-sulfur battery, wherein the battery diaphragm is a lithium-sulfur battery diaphragm with graphene attached on the surface, the battery diaphragm can inhibit the shuttling of lithium polysulfide between the positive electrode and the negative electrode of the battery, and the lithium polysulfide dissolved in electrolyte is reused by utilizing the conductive capacity of the graphene on the surface of the battery diaphragm, so that the utilization rate of battery active substances is improved, and the discharge capacity, cycle life and other performances of the lithium-sulfur battery are improved; the following disadvantages still exist: (1) the battery diaphragm has large fiber diameter, small specific surface area, low electrolyte adsorption rate and poor wettability of the diaphragm; (2) the compounding equipment for compounding the battery diaphragm ensures that the compounding of the battery diaphragm is not tight enough and the quality is not high.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a graphene battery diaphragm and a preparation method thereof: (1) the nanofiber membrane is prepared by a technology of preparing the nanofiber membrane by an electrostatic spinning method, the technology is characterized in that jet flow formed by polymer solution is cracked and refined under the action of a high-voltage electric field, and the nanofiber membrane is formed by solvent volatilization or solution cooling, so that the problems of large fiber diameter, small specific surface area, low electrolyte adsorption rate and poor membrane wettability of the existing battery membrane are solved; (2) guiding a polyvinylidene fluoride-based graphene nanofiber membrane to a position between an extrusion roller and a bearing plate through the top of a guide roller, rotating a hand wheel to drive a limiting plate to descend, pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane, spraying polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by an upper nozzle and a lower nozzle of an electrostatic spinning machine in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through a first guide roller and a second guide roller respectively to form the polyvinylidene fluoride-based polymer nanofiber membrane to obtain a semi-finished graphene membrane, heating and melting the semi-finished graphene membrane when passing through a heating roller, extruding and compounding the semi-finished graphene membrane between an upper compression roller and a lower compression roller, cooling and shaping the semi-finished graphene membrane when passing through a cooling roller to obtain the graphene battery diaphragm, the battery diaphragm compounding device solves the problems that the compounding of the battery diaphragm is not tight enough and the quality is not high in the existing compounding equipment.
The purpose of the invention can be realized by the following technical scheme:
as a further scheme of the invention: a graphene battery diaphragm comprises an upper polyvinylidene fluoride-based polymer nanofiber membrane, a lower polyvinylidene fluoride-based polymer nanofiber membrane and a middle polyvinylidene fluoride-based graphene nanofiber membrane;
the polyvinylidene fluoride-based polymer nanofiber membrane is prepared from the following components in parts by weight: 65-85 parts of polyvinylidene fluoride, 10-25 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5-10 parts of polyacrylonitrile, 15-30 parts of N, N-dimethylformamide, 65-80 parts of dimethylacetamide and 5-30 parts of acetone;
the polyvinylidene fluoride-based graphene nanofiber membrane is prepared from the following components in parts by weight: 40-60 parts of graphite powder, 25-45 parts of concentrated sulfuric acid, 15-25 parts of a mixture of potassium permanganate and sodium nitrate, 10-25 parts of hydrogen peroxide, 1-5 parts of a titanate coupling agent, 10-15 parts of hydrazine hydrate and 10-25 parts of sodium polystyrene sulfonate;
the graphene battery diaphragm is prepared by the following steps:
the method comprises the following steps: preparing polyvinylidene fluoride-based polymer composite solution;
step two: preparing a graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: and obtaining the graphene battery diaphragm.
As a further scheme of the invention: the mass content of the polyvinylidene fluoride base polymer nanofiber membranes of the upper layer and the lower layer respectively accounts for 15-25% of the total mass, and the mass content of the polyvinylidene fluoride base graphene nanofiber membranes accounts for 50-70% of the total mass.
As a further scheme of the invention: a preparation method of a graphene battery diaphragm comprises the following steps:
the method comprises the following steps: preparing a polyvinylidene fluoride-based polymer composite solution:
a1, stirring and uniformly mixing polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer and polyacrylonitrile to obtain a polymer mixture;
a2, fusing N, N-dimethylformamide, dimethylacetamide and acetone, and stirring to form a uniform and transparent mixed solution;
a3, adding the mixed solution into a polymer mixture, stirring, standing for 4-6 hours, stirring by a magnetic stirrer, and obtaining the polyvinylidene fluoride-based polymer composite solution after the viscosity reaches 600-750Pa.s at a low speed of 0.5 and a medium speed of 5-6 hours;
step two: preparing a graphene solution:
b1, adding the graphite powder into a container, adding concentrated sulfuric acid, stirring to fully mix the graphite powder with the concentrated sulfuric acid, adding a mixture of potassium permanganate and sodium nitrate, starting a stirrer, firstly stirring at a low speed for 0.5 hour, putting the container into a freezing water tower, starting at a medium speed for 4-6 hours, adding hydrogen peroxide, and stirring until the color of the solution is changed into golden yellow viscous solution;
b2, putting the golden yellow viscous solution into a centrifugal separator, separating out precipitates, adding a titanate coupling agent, stirring, adding hydrazine hydrate, controlling the temperature to be 80-100 ℃, adding sodium polystyrene sulfonate, stirring for 3-4 hours, washing for 4-6 times with absolute ethyl alcohol, washing for 3-4 times with deionized water, and dispersing for 2-4 hours with ultrasonic waves to obtain a uniform graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane:
c1, adding 30-50 wt% of polyvinylidene fluoride-based polymer composite solution into the graphene solution, stirring with a magnetic stirrer, firstly stirring at a low speed for 0.5 hour, then stirring at a medium speed for 5-6 hours until the viscosity reaches 600-750Pa.s, and standing for 4 hours to obtain the graphene polymer composite solution;
c2, performing electrostatic spinning on the graphene polymer composite solution by using an electrostatic spinning machine to form a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane:
D. guiding the polyvinylidene fluoride-based graphene nanofiber membrane to an extrusion roller and a pressure bearing plate through a guide roller of graphene battery diaphragm composite equipment, rotating a hand wheel to drive a limiting plate to descend, increasing the pressure of the extrusion roller on the pressure bearing plate, and pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: obtaining a graphene battery diaphragm:
e1, respectively installing an upper nozzle and a lower nozzle of an electrostatic spinning machine on the upper mounting plate and the lower mounting plate, filling the rest polyvinylidene fluoride-based polymer composite solution into a liquid tank connected with the upper nozzle and the lower nozzle on the electrostatic spinning machine through pipelines, and respectively spraying the polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by the upper nozzle and the lower nozzle in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller and the second guide roller after pressurization is completed to form the polyvinylidene fluoride-based polymer nanofiber membrane, so as to obtain a semi-finished graphene membrane;
e2, heating and melting the semi-finished graphene film when the semi-finished graphene film passes through a heating roller, extruding and compounding the semi-finished graphene film between an upper pressing roller and a lower pressing roller, and cooling and shaping the semi-finished graphene film when the semi-finished graphene film passes through a cooling roller to obtain the graphene battery diaphragm.
As a further scheme of the invention: the working temperature of electrostatic spinning in the fifth step is 22-25 ℃, the working voltage is 5-50kV, the temperature of an electrostatic spinning area in the electrostatic spinning machine is 21-23 ℃, and the humidity is 28-32%; the width of the polyvinylidene fluoride-based graphene nanofiber membrane is 0.8-1m, and the thickness of the membrane is 6-50 μm.
As a further scheme of the invention: the working process of the graphene battery diaphragm compounding equipment in the fourth step is as follows:
the method comprises the following steps: guiding the polyvinylidene fluoride-based graphene nanofiber membrane to a position between the extrusion roller and the pressure bearing plate through the top of the guide roller, rotating the hand wheel, and driving the linkage shaft to rotate so as to drive the limiting plate to move upwards or downwards, so that the pressure of the extrusion roller on the pressure bearing plate is changed;
step two: in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller and the second guide roller, an upper nozzle and a lower nozzle of an electrostatic spinning machine respectively spray polyvinylidene fluoride-based polymer composite solutions on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane to form the polyvinylidene fluoride-based polymer nanofiber membrane, so that a semi-finished graphene membrane is obtained;
step three: adding clear water into a hot water cavity of the heating roller from the first water inlet pipe, heating the heating pipe to heat and melt the semi-finished graphene film, extruding and compounding the semi-finished graphene film between an upper compression roller and a lower compression roller, adding cold water into a cold water cavity of the cooling roller from the second water inlet pipe, and cooling and shaping the semi-finished graphene film to obtain the graphene battery diaphragm;
step four: the graphene battery diaphragm is guided to the winding roller through the guide roller, the driving motor is started, the driving motor operates to realize rotation of the winding roller through the main belt pulley and the auxiliary belt pulley, and the graphene battery diaphragm is wound.
The invention has the beneficial effects that:
(1) the graphene battery diaphragm is prepared by a technology for preparing a nanofiber diaphragm through an electrostatic spinning method, wherein the technology comprises the steps of cracking and refining jet flow formed by high-molecular solution under the action of a high-voltage electric field, and volatilizing a solvent or cooling the solution to form the nanofiber diaphragm;
the graphene battery diaphragm prepared by adopting the electrostatic spinning method technology comprises the following components: the diameter of the fiber is small (50-150nm), the specific surface area is large, and the electrolyte adsorption rate can reach 450%, so the wettability of the diaphragm is good;
the battery prepared by using the graphene battery diaphragm is detected, and the test result shows that the discharge capacity of the battery at the charge-discharge rate of 0.5C is 914-1021mAh/g, and the discharge capacity after 100 cycles is 782-836 mAh/g;
(2) the invention relates to a preparation method of a graphene battery diaphragm, which comprises the steps of compounding a polyvinylidene fluoride-based polymer nanofiber membrane and a polyvinylidene fluoride-based graphene nanofiber membrane by using a graphene battery diaphragm compounding device, guiding the polyvinylidene fluoride-based graphene nanofiber membrane to a position between an extrusion roller and a pressure bearing plate through the top of a guide roller, rotating a hand wheel to drive a limiting plate to descend, pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane, spraying polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by an upper nozzle and a lower nozzle of an electrostatic spinning machine in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller and the second guide roller to form the polyvinylidene fluoride-based polymer nanofiber membrane to obtain a semi-finished graphene membrane, heating and melting the semi-finished graphene membrane when passing through a heating roller, extruding and compounding the semi-finished graphene film between an upper pressing roller and a lower pressing roller, and cooling and shaping the semi-finished graphene film when the semi-finished graphene film passes through a cooling roller to obtain the graphene battery diaphragm; this graphite alkene battery diaphragm combination equipment pressurizes polyvinylidene fluoride base graphite alkene nanofiber membrane through squeeze roll, bearing plate for the connection is inseparable between the fibre, through warming mill heating melting, through last compression roller, down between the compression roller by extrusion complex, cools off when passing through the chill roll and stereotypes, makes polyvinylidene fluoride base polymer nanofiber membrane and polyvinylidene fluoride base graphite alkene nanofiber membrane complex inseparable, further improves the infiltration nature of diaphragm, makes this graphite alkene battery diaphragm's quality high.
Drawings
The invention will be further described with reference to the accompanying drawings.
Fig. 1 is a top view of a graphene battery separator composite device in accordance with the present invention;
fig. 2 is a schematic view of the internal structure of the graphene battery separator composite device according to the present invention;
FIG. 3 is a connection view of a wind-up roll and a driving motor in the present invention;
FIG. 4 is a schematic view showing the internal structure of a heating roller in the present invention;
fig. 5 is a schematic view of the internal structure of the cooling roll in the present invention.
In the figure: 101. a support plate; 102. a squeeze roll; 103. a hand wheel; 104. a first guide roller; 105. a second guide roller; 106. a heating roller; 107. an upper compression roller; 108. a cooling roll; 109. a wind-up roll; 110. a guide roller; 111. a pressure bearing plate; 112. an upper mounting plate; 113. an upper nozzle; 114. a drive motor; 115. a coil spring; 116. a linkage shaft; 117. a secondary pulley; 118. a limiting plate; 119. a lower mounting plate; 120. a lower nozzle; 121. a lower pressing roller; 122. a primary pulley; 123. a hot water chamber; 124. heating a tube; 125. a first water inlet pipe; 126. an electromagnetic valve; 127. a cold water chamber; 128. a second water inlet pipe; 129. and (4) discharging the guide roller.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
referring to fig. 1-5, the present embodiment is a graphene battery separator, including an upper layer and a lower layer of polyvinylidene fluoride-based polymer nanofiber membrane, and a middle layer of polyvinylidene fluoride-based graphene nanofiber membrane;
the polyvinylidene fluoride-based polymer nanofiber membrane is prepared from the following components in parts by weight: 65 parts of polyvinylidene fluoride, 10 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5 parts of polyacrylonitrile, 15 parts of N, N-dimethylformamide, 65 parts of dimethylacetamide and 5 parts of acetone;
the polyvinylidene fluoride-based graphene nanofiber membrane is prepared from the following components in parts by weight: 40 parts of graphite powder, 25 parts of concentrated sulfuric acid, 15 parts of a mixture of potassium permanganate and sodium nitrate, 10 parts of hydrogen peroxide, 1 part of a titanate coupling agent, 10 parts of hydrazine hydrate and 10 parts of sodium polystyrene sulfonate;
the graphene battery diaphragm is prepared by the following steps:
the method comprises the following steps: preparing polyvinylidene fluoride-based polymer composite solution;
step two: preparing a graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: and obtaining the graphene battery diaphragm.
The mass content of the polyvinylidene fluoride base polymer nanofiber membranes of the upper layer and the lower layer respectively accounts for 15-25% of the total mass, and the mass content of the polyvinylidene fluoride base graphene nanofiber membranes accounts for 50-70% of the total mass.
A preparation method of a graphene battery diaphragm comprises the following steps:
the method comprises the following steps: preparing a polyvinylidene fluoride-based polymer composite solution:
a1, stirring and uniformly mixing polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer and polyacrylonitrile to obtain a polymer mixture;
a2, fusing N, N-dimethylformamide, dimethylacetamide and acetone, and stirring to form a uniform and transparent mixed solution;
a3, adding the mixed solution into a polymer mixture, stirring, standing for 4-6 hours, stirring by a magnetic stirrer, and obtaining the polyvinylidene fluoride-based polymer composite solution after the viscosity reaches 600-750Pa.s at a low speed of 0.5 and a medium speed of 5-6 hours;
step two: preparing a graphene solution:
b1, adding the graphite powder into a container, adding concentrated sulfuric acid, stirring to fully mix the graphite powder with the concentrated sulfuric acid, adding a mixture of potassium permanganate and sodium nitrate, starting a stirrer, firstly stirring at a low speed for 0.5 hour, putting the container into a freezing water tower, starting at a medium speed for 4-6 hours, adding hydrogen peroxide, and stirring until the color of the solution is changed into golden yellow viscous solution;
b2, putting the golden yellow viscous solution into a centrifugal separator, separating out precipitates, adding a titanate coupling agent, stirring, adding hydrazine hydrate, controlling the temperature to be 80-100 ℃, adding sodium polystyrene sulfonate, stirring for 3-4 hours, washing for 4-6 times with absolute ethyl alcohol, washing for 3-4 times with deionized water, and dispersing for 2-4 hours with ultrasonic waves to obtain a uniform graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane:
c1, adding 30-50 wt% of polyvinylidene fluoride-based polymer composite solution into the graphene solution, stirring with a magnetic stirrer, firstly stirring at a low speed for 0.5 hour, then stirring at a medium speed for 5-6 hours until the viscosity reaches 600-750Pa.s, and standing for 4 hours to obtain the graphene polymer composite solution;
c2, performing electrostatic spinning on the graphene polymer composite solution by using an electrostatic spinning machine to form a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane:
D. guiding the polyvinylidene fluoride-based graphene nanofiber membrane to an extrusion roller 102 and a pressure bearing plate 111 through a guide roller 110 of graphene battery diaphragm composite equipment, rotating a hand wheel 103 to drive a limiting plate 118 to descend, increasing the pressure of the extrusion roller 102 on the pressure bearing plate 111, and pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: obtaining a graphene battery diaphragm:
e1, respectively installing an upper nozzle 113 and a lower nozzle 120 of an electrostatic spinning machine on an upper installation plate 112 and a lower installation plate 119, filling the rest polyvinylidene fluoride-based polymer composite solution into a liquid tank on the electrostatic spinning machine, which is connected with the upper nozzle 113 and the lower nozzle 120 through pipelines, and respectively spraying the polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by the upper nozzle 113 and the lower nozzle 120 in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller 104 to the second guide roller 105 after pressurization is completed to form the polyvinylidene fluoride-based polymer nanofiber membrane, so as to obtain a semi-finished graphene membrane;
e2, heating and melting the semi-finished graphene film when the semi-finished graphene film passes through the heating roller 106, extruding and compounding the semi-finished graphene film between the upper pressing roller 107 and the lower pressing roller 121, and cooling and shaping the semi-finished graphene film when the semi-finished graphene film passes through the cooling roller 108 to obtain the graphene battery diaphragm.
In the fifth step, the working temperature of electrostatic spinning is 22-25 ℃, the working voltage is 5-50kV, the temperature of an electrostatic spinning area in the electrostatic spinning machine is 21-23 ℃, and the humidity is 28-32%; the width of the polyvinylidene fluoride-based graphene nanofiber membrane is 0.8-1m, and the thickness of the membrane is 6-50 μm.
When the battery prepared by using the graphene battery diaphragm of the example 1 is detected, the discharge capacity of the battery at the charge and discharge rate of 0.5C is 914mAh/g, and the discharge capacity after 100 cycles is 782 mAh/g.
Example 2:
referring to fig. 1-5, the present embodiment is a graphene battery separator, including an upper layer and a lower layer of polyvinylidene fluoride-based polymer nanofiber membrane, and a middle layer of polyvinylidene fluoride-based graphene nanofiber membrane;
the polyvinylidene fluoride-based polymer nanofiber membrane is prepared from the following components in parts by weight: 85 parts of polyvinylidene fluoride, 25 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 10 parts of polyacrylonitrile, 30 parts of N, N-dimethylformamide, 80 parts of dimethylacetamide and 30 parts of acetone;
the polyvinylidene fluoride-based graphene nanofiber membrane is prepared from the following components in parts by weight: 60 parts of graphite powder, 45 parts of concentrated sulfuric acid, 25 parts of a mixture of potassium permanganate and sodium nitrate, 25 parts of hydrogen peroxide, 5 parts of a titanate coupling agent, 15 parts of hydrazine hydrate and 25 parts of sodium polystyrene sulfonate;
the graphene battery diaphragm is prepared by the following steps:
the method comprises the following steps: preparing polyvinylidene fluoride-based polymer composite solution;
step two: preparing a graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: and obtaining the graphene battery diaphragm.
The mass content of the polyvinylidene fluoride base polymer nanofiber membranes of the upper layer and the lower layer respectively accounts for 15-25% of the total mass, and the mass content of the polyvinylidene fluoride base graphene nanofiber membranes accounts for 50-70% of the total mass.
A preparation method of a graphene battery diaphragm comprises the following steps:
the method comprises the following steps: preparing a polyvinylidene fluoride-based polymer composite solution:
a1, stirring and uniformly mixing polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer and polyacrylonitrile to obtain a polymer mixture;
a2, fusing N, N-dimethylformamide, dimethylacetamide and acetone, and stirring to form a uniform and transparent mixed solution;
a3, adding the mixed solution into a polymer mixture, stirring, standing for 4-6 hours, stirring by a magnetic stirrer, and obtaining the polyvinylidene fluoride-based polymer composite solution after the viscosity reaches 600-750Pa.s at a low speed of 0.5 and a medium speed of 5-6 hours;
step two: preparing a graphene solution:
b1, adding the graphite powder into a container, adding concentrated sulfuric acid, stirring to fully mix the graphite powder with the concentrated sulfuric acid, adding a mixture of potassium permanganate and sodium nitrate, starting a stirrer, firstly stirring at a low speed for 0.5 hour, putting the container into a freezing water tower, starting at a medium speed for 4-6 hours, adding hydrogen peroxide, and stirring until the color of the solution is changed into golden yellow viscous solution;
b2, putting the golden yellow viscous solution into a centrifugal separator, separating out precipitates, adding a titanate coupling agent, stirring, adding hydrazine hydrate, controlling the temperature to be 80-100 ℃, adding sodium polystyrene sulfonate, stirring for 3-4 hours, washing for 4-6 times with absolute ethyl alcohol, washing for 3-4 times with deionized water, and dispersing for 2-4 hours with ultrasonic waves to obtain a uniform graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane:
c1, adding 30-50 wt% of polyvinylidene fluoride-based polymer composite solution into the graphene solution, stirring with a magnetic stirrer, firstly stirring at a low speed for 0.5 hour, then stirring at a medium speed for 5-6 hours until the viscosity reaches 600-750Pa.s, and standing for 4 hours to obtain the graphene polymer composite solution;
c2, performing electrostatic spinning on the graphene polymer composite solution by using an electrostatic spinning machine to form a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane:
D. guiding the polyvinylidene fluoride-based graphene nanofiber membrane to an extrusion roller 102 and a pressure bearing plate 111 through a guide roller 110 of graphene battery diaphragm composite equipment, rotating a hand wheel 103 to drive a limiting plate 118 to descend, increasing the pressure of the extrusion roller 102 on the pressure bearing plate 111, and pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: obtaining a graphene battery diaphragm:
e1, respectively installing an upper nozzle 113 and a lower nozzle 120 of an electrostatic spinning machine on an upper installation plate 112 and a lower installation plate 119, filling the rest polyvinylidene fluoride-based polymer composite solution into a liquid tank on the electrostatic spinning machine, which is connected with the upper nozzle 113 and the lower nozzle 120 through pipelines, and respectively spraying the polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by the upper nozzle 113 and the lower nozzle 120 in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller 104 to the second guide roller 105 after pressurization is completed to form the polyvinylidene fluoride-based polymer nanofiber membrane, so as to obtain a semi-finished graphene membrane;
e2, heating and melting the semi-finished graphene film when the semi-finished graphene film passes through the heating roller 106, extruding and compounding the semi-finished graphene film between the upper pressing roller 107 and the lower pressing roller 121, and cooling and shaping the semi-finished graphene film when the semi-finished graphene film passes through the cooling roller 108 to obtain the graphene battery diaphragm.
In the fifth step, the working temperature of electrostatic spinning is 22-25 ℃, the working voltage is 5-50kV, the temperature of an electrostatic spinning area in the electrostatic spinning machine is 21-23 ℃, and the humidity is 28-32%; the width of the polyvinylidene fluoride-based graphene nanofiber membrane is 0.8-1m, and the thickness of the membrane is 6-50 μm.
When the battery prepared by using the graphene battery diaphragm of example 2 is tested, the discharge capacity of the battery at the charge and discharge rate of 0.5C is 1021mAh/g, and the discharge capacity after 100 cycles is 836 mAh/g.
Example 3:
referring to fig. 1 to 5, the graphene battery separator compositing apparatus in this embodiment includes a supporting plate 101, a pressing roller 102, a heating roller 106, and a cooling roller 108, wherein a guiding roller 110 is installed between one end of the supporting plate 101 at two sides, a supporting plate 111 is installed at one side of the guiding roller 110, the pressing roller 102 is installed above the supporting plate 111, a first guiding roller 104 is installed at one side of the pressing roller 102 away from the guiding roller 110, a second guiding roller 105 is installed at one side of the first guiding roller 104 away from the supporting plate 111 side by side, an upper mounting plate 112 and a lower mounting plate 119 are respectively installed at upper and lower sides between the first guiding roller 104 and the second guiding roller 105, the heating roller 106 is installed at an oblique lower side of one side of the second guiding roller 105 away from the first guiding roller 104, an upper pressing roller 107 and a cooling roller 108 are sequentially installed at one side of the heating roller 106 away from the second guiding roller, a lower pressing roller 121 is installed at the bottom of the upper pressing roller 107, an outlet guide roller 129 is installed above the cooling roller 108 away from the lower pressing roller 121 in an inclined manner, a winding roller 109 is installed on the outlet guide roller 129 away from the cooling roller 108 in parallel, and a driving motor 114 is installed right below the winding roller 109;
limiting plates 118 are mounted right above shafts at two ends of the extrusion roller 102, a linkage shaft 116 is mounted at the top end of each limiting plate 118, threads are arranged on the linkage shaft 116, the top end of each linkage shaft 116 penetrates through the support plate 101 and is provided with a hand wheel 103, a spiral spring 115 is arranged between each hand wheel 103 and the support plate 101, and the spiral spring 115 is sleeved on the linkage shaft 116;
the upper mounting plate 112 is used for mounting an upper nozzle 113 of the electrostatic spinning machine, and the lower mounting plate 119 is used for mounting a lower nozzle 120 of the electrostatic spinning machine;
an auxiliary belt pulley 117 and a main belt pulley 122 are arranged in the inner cavity of the supporting plate 101 on one side, the auxiliary belt pulley 117 is sleeved on one end of the winding roller 109 shaft, the main belt pulley 122 is sleeved on an output shaft of the driving motor 114, and the auxiliary belt pulley 117 is connected with the main belt pulley 122 through a belt;
the heating roller 106 is internally provided with a hot water cavity 123, the middle part of the hot water cavity 123 is horizontally provided with a heating pipe 124, one end of the heating roller 106 is provided with a first water inlet pipe 125, the first water inlet pipe 125 is communicated with the hot water cavity 123, the cooling roller 108 is internally provided with a cold water cavity 127, one end of the cooling roller 108 is provided with a second water inlet pipe 128, the second water inlet pipe 128 is communicated with the cold water cavity 127, and the first water inlet pipe 125 and the second water inlet pipe 128 are both provided with an electromagnetic valve 126.
Referring to fig. 1 to 5, the working process of the graphene battery separator composite device in the present embodiment is as follows:
the method comprises the following steps: guiding the polyvinylidene fluoride-based graphene nanofiber membrane between the extrusion roller 102 and the pressure bearing plate 111 through the top of the guide roller 110, rotating the hand wheel 103 to drive the linkage shaft 116 to rotate so as to drive the limiting plate 118 to move upwards or downwards, and thus changing the pressure of the extrusion roller 102 on the pressure bearing plate 111;
step two: in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through the first guide roller 104 to the second guide roller 105, an upper nozzle 113 and a lower nozzle 120 of an electrostatic spinning machine respectively spray polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane to form the polyvinylidene fluoride-based polymer nanofiber membrane, so that a semi-finished graphene membrane is obtained;
step three: adding clear water into a hot water cavity 123 of the heating roller 106 from a first water inlet pipe 125, heating the heating pipe 124 to heat and melt the semi-finished graphene film, extruding and compounding the semi-finished graphene film between an upper pressing roller 107 and a lower pressing roller 121, adding cold water into a cold water cavity 127 of the cooling roller 108 from a second water inlet pipe 128, and cooling and shaping the semi-finished graphene film to obtain the graphene battery diaphragm;
step four: the graphene battery diaphragm is guided to the take-up roll 109 through the discharge guide roll 129, the driving motor 114 is started, the driving motor 114 runs through the main belt pulley 122 and the auxiliary belt pulley 117 to realize the rotation of the take-up roll 109, and the graphene battery diaphragm is wound.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. A graphene battery diaphragm is characterized by comprising an upper polyvinylidene fluoride-based polymer nanofiber membrane, a lower polyvinylidene fluoride-based polymer nanofiber membrane and a middle polyvinylidene fluoride-based graphene nanofiber membrane;
the polyvinylidene fluoride-based polymer nanofiber membrane is prepared from the following components in parts by weight: 65-85 parts of polyvinylidene fluoride, 10-25 parts of polyvinylidene fluoride-hexafluoropropylene copolymer, 5-10 parts of polyacrylonitrile, 15-30 parts of N, N-dimethylformamide, 65-80 parts of dimethylacetamide and 5-30 parts of acetone;
the polyvinylidene fluoride-based graphene nanofiber membrane is prepared from the following components in parts by weight: 40-60 parts of graphite powder, 25-45 parts of concentrated sulfuric acid, 15-25 parts of a mixture of potassium permanganate and sodium nitrate, 10-25 parts of hydrogen peroxide, 1-5 parts of a titanate coupling agent, 10-15 parts of hydrazine hydrate and 10-25 parts of sodium polystyrene sulfonate;
the graphene battery diaphragm is prepared by the following steps:
the method comprises the following steps: preparing polyvinylidene fluoride-based polymer composite solution;
step two: preparing a graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: and obtaining the graphene battery diaphragm.
2. The graphene battery separator according to claim 1, wherein the polyvinylidene fluoride-based polymer nanofiber membranes of the upper and lower layers respectively account for 15-25% of the total mass, and the polyvinylidene fluoride-based graphene nanofiber membranes account for 50-70% of the total mass.
3. A preparation method of a graphene battery diaphragm is characterized by comprising the following steps:
the method comprises the following steps: preparing a polyvinylidene fluoride-based polymer composite solution:
a1, stirring and uniformly mixing polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer and polyacrylonitrile to obtain a polymer mixture;
a2, fusing N, N-dimethylformamide, dimethylacetamide and acetone, and stirring to form a uniform and transparent mixed solution;
a3, adding the mixed solution into a polymer mixture, stirring, standing for 4-6 hours, stirring by a magnetic stirrer, and obtaining the polyvinylidene fluoride-based polymer composite solution after the viscosity reaches 600-750Pa.s at a low speed of 0.5 and a medium speed of 5-6 hours;
step two: preparing a graphene solution:
b1, adding the graphite powder into a container, adding concentrated sulfuric acid, stirring to fully mix the graphite powder with the concentrated sulfuric acid, adding a mixture of potassium permanganate and sodium nitrate, starting a stirrer, firstly stirring at a low speed for 0.5 hour, putting the container into a freezing water tower, starting at a medium speed for 4-6 hours, adding hydrogen peroxide, and stirring until the color of the solution is changed into golden yellow viscous solution;
b2, putting the golden yellow viscous solution into a centrifugal separator, separating out precipitates, adding a titanate coupling agent, stirring, adding hydrazine hydrate, controlling the temperature to be 80-100 ℃, adding sodium polystyrene sulfonate, stirring for 3-4 hours, washing for 4-6 times with absolute ethyl alcohol, washing for 3-4 times with deionized water, and dispersing for 2-4 hours with ultrasonic waves to obtain a uniform graphene solution;
step three: preparing a polyvinylidene fluoride-based graphene nanofiber membrane:
c1, adding 30-50 wt% of polyvinylidene fluoride-based polymer composite solution into the graphene solution, stirring with a magnetic stirrer, firstly stirring at a low speed for 0.5 hour, then stirring at a medium speed for 5-6 hours until the viscosity reaches 600-750Pa.s, and standing for 4 hours to obtain the graphene polymer composite solution;
c2, performing electrostatic spinning on the graphene polymer composite solution by using an electrostatic spinning machine to form a polyvinylidene fluoride-based graphene nanofiber membrane;
step four: pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane:
D. guiding the polyvinylidene fluoride-based graphene nanofiber membrane to an extrusion roller (102) and a pressure bearing plate (111) through a guide roller (110) of graphene battery diaphragm composite equipment, rotating a hand wheel (103), driving a limiting plate (118) to descend, increasing the pressure of the extrusion roller (102) on the pressure bearing plate (111), and pressurizing the polyvinylidene fluoride-based graphene nanofiber membrane;
step five: obtaining a graphene battery diaphragm:
e1, respectively installing an upper nozzle (113) and a lower nozzle (120) of an electrostatic spinning machine on an upper installation plate (112) and a lower installation plate (119), filling the rest polyvinylidene fluoride-based polymer composite solution into a liquid tank connected with the upper nozzle (113) and the lower nozzle (120) on the electrostatic spinning machine through pipelines, and spraying the polyvinylidene fluoride-based polymer composite solution on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane by the upper nozzle (113) and the lower nozzle (120) respectively to form the polyvinylidene fluoride-based polymer nanofiber membrane in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through a first guide roller (104) to a second guide roller (105) after pressurization is completed, so as to obtain a semi-finished graphene membrane;
e2, heating and melting the semi-finished graphene film when the semi-finished graphene film passes through a heating roller (106), extruding and compounding the semi-finished graphene film between an upper pressing roller (107) and a lower pressing roller (121), and cooling and shaping the semi-finished graphene film when the semi-finished graphene film passes through a cooling roller (108) to obtain the graphene battery diaphragm.
4. The preparation method of the graphene battery separator according to claim 3, wherein the working temperature of electrostatic spinning in the fifth step is 22-25 ℃, the working voltage is 5-50kV, the temperature of an electrostatic spinning zone in the electrostatic spinning machine is 21-23 ℃, and the humidity is 28-32%; the width of the polyvinylidene fluoride-based graphene nanofiber membrane is 0.8-1m, and the thickness of the membrane is 6-50 μm.
5. The method for preparing the graphene battery diaphragm according to claim 3, wherein the working process of the graphene battery diaphragm compounding device in the fourth step is as follows:
the method comprises the following steps: guiding the polyvinylidene fluoride-based graphene nanofiber membrane to a position between the extrusion roller (102) and the pressure bearing plate (111) through the top of the guide roller (110), rotating the hand wheel (103), and driving the linkage shaft (116) to rotate so as to drive the limiting plate (118) to move upwards or downwards, so that the pressure of the extrusion roller (102) on the pressure bearing plate (111) is changed;
step two: in the process that the polyvinylidene fluoride-based graphene nanofiber membrane passes through a first guide roller (104) to a second guide roller (105), an upper nozzle (113) and a lower nozzle (120) of an electrostatic spinning machine respectively spray polyvinylidene fluoride-based polymer composite solutions on the upper surface and the lower surface of the polyvinylidene fluoride-based graphene nanofiber membrane to form the polyvinylidene fluoride-based polymer nanofiber membrane, so that a semi-finished graphene membrane is obtained;
step three: adding clean water into a hot water cavity (123) of a heating roller (106) from a first water inlet pipe (125), heating a heating pipe (124) to heat and melt a semi-finished graphene film, extruding and compounding the semi-finished graphene film between an upper pressing roller (107) and a lower pressing roller (121), adding cold water into a cold water cavity (127) of a cooling roller (108) from a second water inlet pipe (128), and cooling and shaping the semi-finished graphene film to obtain the graphene battery diaphragm;
step four: the graphene battery diaphragm is guided to a winding roller (109) through a guide roller (129), a driving motor (114) is started, the driving motor (114) runs through a main belt pulley (122) and an auxiliary belt pulley (117) to realize the rotation of the winding roller (109), and the graphene battery diaphragm is wound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010277795.6A CN111477822A (en) | 2020-04-08 | 2020-04-08 | Graphene battery diaphragm and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010277795.6A CN111477822A (en) | 2020-04-08 | 2020-04-08 | Graphene battery diaphragm and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111477822A true CN111477822A (en) | 2020-07-31 |
Family
ID=71751460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010277795.6A Pending CN111477822A (en) | 2020-04-08 | 2020-04-08 | Graphene battery diaphragm and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111477822A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047331A (en) * | 2020-09-17 | 2020-12-08 | 常州机电职业技术学院 | High-voltage discharge graphene condensed beam vacuum preparation equipment |
| CN112575444A (en) * | 2020-11-23 | 2021-03-30 | 南通纺织丝绸产业技术研究院 | High-protection high-moisture-permeability nanofiber membrane and preparation of medical protective equipment thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090169725A1 (en) * | 2008-01-02 | 2009-07-02 | Aruna Zhamu | Method of producing hybrid nano-filament electrodes for lithium metal or lithium ion batteries |
| CN203358001U (en) * | 2013-07-16 | 2013-12-25 | 莱州联友金浩新型材料有限公司 | Lamination composite equipment for porous battery diaphragm material |
| CN106450118A (en) * | 2016-11-01 | 2017-02-22 | 浙江大东南集团有限公司 | Lithium ion battery nanofiber graphene composite membrane and preparation method thereof |
| CN109888156A (en) * | 2019-03-15 | 2019-06-14 | 深圳集智云创科技开发有限公司 | A kind of composite lithium ion cell diaphragm and its preparation process |
-
2020
- 2020-04-08 CN CN202010277795.6A patent/CN111477822A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090169725A1 (en) * | 2008-01-02 | 2009-07-02 | Aruna Zhamu | Method of producing hybrid nano-filament electrodes for lithium metal or lithium ion batteries |
| CN203358001U (en) * | 2013-07-16 | 2013-12-25 | 莱州联友金浩新型材料有限公司 | Lamination composite equipment for porous battery diaphragm material |
| CN106450118A (en) * | 2016-11-01 | 2017-02-22 | 浙江大东南集团有限公司 | Lithium ion battery nanofiber graphene composite membrane and preparation method thereof |
| CN109888156A (en) * | 2019-03-15 | 2019-06-14 | 深圳集智云创科技开发有限公司 | A kind of composite lithium ion cell diaphragm and its preparation process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112047331A (en) * | 2020-09-17 | 2020-12-08 | 常州机电职业技术学院 | High-voltage discharge graphene condensed beam vacuum preparation equipment |
| CN112575444A (en) * | 2020-11-23 | 2021-03-30 | 南通纺织丝绸产业技术研究院 | High-protection high-moisture-permeability nanofiber membrane and preparation of medical protective equipment thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106450101B (en) | A method of preparing lithium battery diaphragm with coaxial electrostatic spinning | |
| JP5031836B2 (en) | Separation membrane having heat-resistant ultrafine fiber layer and secondary battery using the same | |
| CN106450118B (en) | A kind of lithium ion cell nano graphite fiber alkene composite diaphragm and preparation method thereof | |
| JP5924540B2 (en) | Heat resistance, high-strength ultrafine fiber separation membrane, method for producing the same, and secondary battery using the same | |
| CN110993892B (en) | Flexible lithium metal negative electrode framework material and preparation method and application thereof | |
| JP2010500717A (en) | Heat-resistant ultrafine fiber separation membrane and secondary battery using the same | |
| CN111477822A (en) | Graphene battery diaphragm and preparation method thereof | |
| CN110854343B (en) | Preparation method of skin-core structure cellulose modified nanofiber lithium battery diaphragm | |
| CN113506949B (en) | Preparation method of aramid nanofiber-based battery diaphragm with micro-nano porous structure | |
| US20150044574A1 (en) | Polymer electrolyte membranes for rechargeable batteries | |
| JP5130700B2 (en) | Battery electrode manufacturing method and secondary battery | |
| CN112768834A (en) | Method for preparing polyacrylonitrile/sulfonated polyether ether ketone lithium-sulfur battery diaphragm material by electrostatic spinning | |
| CN114649560A (en) | Zn-MOF/PAN @ PAN composite membrane material and preparation method and application thereof | |
| CN110444719A (en) | A kind of high-strength composite lithium ion battery separator | |
| CN115473000B (en) | Battery separator, preparation method thereof and battery | |
| CN116845348A (en) | Nanogel electrolyte of flexible three-dimensional network and preparation method and application thereof | |
| KR101371061B1 (en) | 2-layer seperator for secondary cell with excellent heat-resisting property and its method | |
| CN113140871B (en) | Diaphragm of self-supporting structure for lithium-sulfur battery and preparation method of diaphragm | |
| CN109390534A (en) | A kind of nano fibrous membrane and preparation method thereof for lithium ion battery separator | |
| JP5440668B2 (en) | Battery electrode | |
| CN105514323B (en) | A kind of preparation method of novel high-performance Static Spinning poly (aryl ether sulfone ketone) lithium battery diaphragm | |
| CN116053396B (en) | Manufacturing process of sodium ion battery | |
| CN112290163B (en) | Modified three-layer co-extrusion diaphragm of lithium-sulfur battery and preparation method and application thereof | |
| CN115101887B (en) | Lithium ion battery diaphragm and preparation method and application thereof | |
| Khodaverdi et al. | The Effect of Different Ratios of Malonic Acid to Plyvinylalcohol on Electrochemical and Mechanical Properties of Polyacrylonitrile Electrospun Separators in Lithium-Ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200731 |