CN115939671A - Battery and battery preparation method - Google Patents
Battery and battery preparation method Download PDFInfo
- Publication number
- CN115939671A CN115939671A CN202310244134.7A CN202310244134A CN115939671A CN 115939671 A CN115939671 A CN 115939671A CN 202310244134 A CN202310244134 A CN 202310244134A CN 115939671 A CN115939671 A CN 115939671A
- Authority
- CN
- China
- Prior art keywords
- diaphragm
- battery
- modified
- carbon
- mixture
- 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
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 238000000576 coating method Methods 0.000 claims abstract description 70
- 239000012528 membrane Substances 0.000 claims abstract description 48
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 46
- 239000003575 carbonaceous material Substances 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- 229910010272 inorganic material Inorganic materials 0.000 claims description 29
- 239000011147 inorganic material Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 22
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 19
- 238000000967 suction filtration Methods 0.000 claims description 19
- -1 polyethylene Polymers 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 12
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 26
- 230000005540 biological transmission Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 229920001021 polysulfide Polymers 0.000 description 12
- 239000005077 polysulfide Substances 0.000 description 12
- 150000008117 polysulfides Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000037427 ion transport Effects 0.000 description 3
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a battery and a battery preparation method, which relate to the technical field of batteries, wherein the battery comprises a battery core and electrolyte, the battery core comprises a positive pole piece, a negative pole piece and a modified diaphragm which are stacked or wound, the modified diaphragm is positioned between the positive pole piece and the negative pole piece, wherein the surface of the modified diaphragm is coated with a carbon coating, and the surface of the modified diaphragm is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups; the modified membrane is obtained by the following steps: placing the initial diaphragm in an alcohol mixed water bath for carrying out first ultrasonic treatment; placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment; and drying the diaphragm subjected to the second ultrasonic treatment. According to the invention, the diaphragm is treated by ultraviolet light, so that the thickness of the carbon coating of the diaphragm is reduced, the transmission rate of lithium ions can be increased, and the energy density of the battery is further increased.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a battery and a battery preparation method.
Background
In the use process of the lithium battery, polysulfide migrates back and forth between the positive electrode and the negative electrode of the battery, active substances of the positive electrode are consumed, and the cycle performance of the battery is reduced. In the related art, migration of polysulfides is reduced by coating a carbon material on a separator. However, in the related art, the carbon material needs to be uniformly coated on the surface of the separator, and the coating layer may reduce the lithium ion transport rate, resulting in a low energy density of the battery.
It can be seen that the related art has a problem in that the energy density of the battery is low.
Disclosure of Invention
The embodiment of the invention provides a battery and a battery preparation method, which aim to solve the problem that the energy density of the battery is low in the related technology.
In order to solve the problems, the invention is realized as follows:
in a first aspect, an embodiment of the present invention provides a battery, including a battery cell and an electrolyte, where the battery cell includes a stacked or wound positive electrode plate, a negative electrode plate, and a modified diaphragm, and the modified diaphragm is located between the positive electrode plate and the negative electrode plate, where,
the surface of the modified diaphragm is coated with a carbon coating, and the surface of the modified diaphragm is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups;
the modified diaphragm is obtained by the following steps:
placing the initial diaphragm in an alcohol mixed water bath for carrying out first ultrasonic treatment;
placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment;
and drying the diaphragm subjected to the second ultrasonic treatment.
Optionally, the carbon coating has a thickness of not less than 0.1 μm.
Optionally, the carbon coating comprises a carbon material or a carbon composite comprising the carbon material and an inorganic material, wherein,
the carbon material comprises at least one of acetylene black, ketjen black, carbon nanotubes, graphene and graphene oxide;
the inorganic material comprises at least one of nano-silicon, silicon monoxide, silicon dioxide, tungsten disulfide, molybdenum disulfide and montmorillonite.
Optionally, in a case where the carbon coating layer includes the carbon composite material, a mass ratio of the inorganic material to the carbon material is 2.5.
Optionally, the modified diaphragm is one of a polyethylene diaphragm, a polypropylene diaphragm or a polyethylene/polypropylene diaphragm mixed diaphragm.
Optionally, the volume ratio of alcohol to water is 0.2.
Optionally, the carbon coating is obtained by:
mixing the material of the carbon coating with a binder;
adding a solvent into the mixed mixture, and grinding the mixture until the mixture is dispersed;
adding the dispersed mixture into the solvent for dilution;
carrying out ultrasonic treatment on the diluted mixture;
filtering the mixture subjected to ultrasonic treatment on the modified diaphragm, and drying;
wherein the concentration of the diluted mixture is 0.1mg/mL to 1mg/mL.
Optionally, the adhesive includes at least one of polyvinylidene fluoride, polyethylene oxide, polyacrylic acid, and polyvinyl alcohol;
the solvent includes at least one of dimethylformamide or N-methylpyrrolidone.
Optionally, the electrolyte comprises 1,3 dioxolane, ethylene glycol dimethyl ether, lithium bistrifluoromethanesulfonimide and lithium nitrate, wherein,
the mass ratio of the 1,3 dioxolane to the glyme is 1;
the content of the lithium bis (trifluoromethanesulfonyl) imide is 1mol/L;
the content of the lithium nitrate is 0.2wt%.
In a second aspect, an embodiment of the present invention further provides a battery manufacturing method, including:
placing the initial diaphragm in an alcohol mixed water bath for ultrasonic treatment to obtain a first intermediate diaphragm;
placing the first intermediate diaphragm in ultraviolet rays, water vapor and ozone for ultrasonic treatment to obtain a second intermediate diaphragm;
drying the second middle diaphragm to obtain a modified diaphragm;
mixing a carbon material or a carbon composite material with a binder, and adding a solvent for grinding to obtain a ground first mixture;
adding the solvent into the first mixture for dilution to obtain a second mixture;
carrying out suction filtration and drying on the second mixture and the modified diaphragm to obtain a carbon coating coated on the modified diaphragm;
stacking or convolving the positive pole piece, the negative pole piece and the modified diaphragm to obtain a battery core;
and preparing the battery according to the battery core and the electrolyte.
In the present example, the first sonication was performed by placing the initial membrane in an alcohol-mixed water bath; placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment; and drying the diaphragm subjected to the secondary ultrasonic treatment to obtain a modified diaphragm, wherein the surface of the modified diaphragm is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups, and the hydroxyl groups and/or the carboxyl groups can be tightly attached to the carbon coating, so that the thickness of the carbon coating is reduced, the transmission rate of lithium ions is further improved, and the energy density of the battery is improved.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments of the present invention will be briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and for those skilled in the art, other drawings may be obtained according to the drawings without inventive labor.
Fig. 1 is a schematic structural diagram of a battery provided in an embodiment of the present invention;
fig. 2 is a flow chart of a method for manufacturing a battery according to an embodiment of the present invention;
FIG. 3 is a Fourier infrared plot provided by an embodiment of the present invention;
FIG. 4 is a graph of battery rate provided by an embodiment of the present invention;
fig. 5 is a graph of long cycle performance of a battery provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. 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.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a battery according to an embodiment of the present invention, as shown in fig. 1, the battery includes a battery cell 10 and an electrolyte 20, where the battery cell 10 includes a positive electrode tab 101, a negative electrode tab 102, and a modified diaphragm 1031, and the modified diaphragm 1031 is located between the positive electrode tab 101 and the negative electrode tab 102, where,
the surface of the modified membrane 1031 is coated with a carbon coating 1032, and the surface of the modified membrane 1031 is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups;
the modified membrane 1031 is obtained by:
placing the initial diaphragm in an alcohol mixed water bath for carrying out first ultrasonic treatment;
placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment;
and drying the diaphragm subjected to the second ultrasonic treatment.
The carbon coating 1032 is a porous structure for adsorbing polysulfide to reduce the shuttling effect of the battery. Polysulfide (Li) is dissolved in the battery, and a concentration difference phenomenon exists in the electrolyte 20 during the battery circulation, so that a shuttle effect, namely polysulfide (Li) exists between the anode and the cathode of the battery 2 S x ) The electrolyte migrates back and forth between the positive electrode and the negative electrode, and consumes the positive electrode active substances, so that the cycle of the battery is rapidly reduced. By coating the carbon coating 1032 on the separator, polysulfides are adsorbed by the porous structure of the carbon coating 1032, so that the shuttle effect is reduced, and the cycle performance of the battery is improved.
Due to the action of the coating, the modified diaphragm 1031 can prevent the phenomenon that the negative electrode and the positive electrode are in contact to cause short circuit because the negative electrode is pierced through the diaphragm by the growth of the lithium dendrite, so that the safety performance of the battery is improved.
The modified membrane 1031 has a plurality of hydroxyl groups (R-OH) and/or a plurality of carboxyl groups (R-COOH) on the surface thereof, and the plurality of hydroxyl groups and/or the plurality of carboxyl groups can be tightly bonded to the carbon coating 1032, so that uniform coating can be achieved with a thinner thickness when the carbon coating 1032 is applied, and the modified membrane 1031 has a certain mechanical strength; meanwhile, the thinner carbon coating 1032 can increase the transmission speed of lithium ions, thereby increasing the energy density of the battery.
Specifically, the modified diaphragm 1031 is obtained by ozone polarization treatment, and the process is as follows:
placing the initial diaphragm in an alcohol mixed water bath for carrying out first ultrasonic treatment;
placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment;
and drying the diaphragm subjected to the second ultrasonic treatment.
Wherein the time of the first ultrasonic treatment is 30min to 60min, the time of the second ultrasonic treatment is 2min to 10min, the ultrasonic frequency is 20kHz to 50kHz, the flow of water vapor is 1L/min to 5L/min, and the distance between a diaphragm and an ultraviolet lamp is 5cm to 10cm.
After the above treatment, a plurality of hydroxyl groups and/or a plurality of carboxyl groups are generated on the surface of the membrane, and the modified membrane 1031 is obtained.
In the present example, the first sonication was performed by placing the initial membrane in an alcohol-mixed water bath; placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment; and drying the membrane subjected to the secondary ultrasonic treatment to obtain a modified membrane 1031, wherein the surface of the modified membrane 1031 is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups, and the plurality of hydroxyl groups and/or the plurality of carboxyl groups can be tightly attached to the carbon coating 1032, so that the thickness of the carbon coating 1032 is reduced, the transmission rate of lithium ions is further improved, and the energy density of the battery is improved.
Optionally, the modified membrane 1031 has a thickness of 40 μm to 80 μm, and the carbon coating 1032 has a thickness of not less than 0.1 μm.
The thickness of the modified membrane 1031 is similar to that of the original membrane, and the thickness change is small after ozone polarization treatment, and the thickness is usually 40 μm to 80 μm, so that lithium ions can pass through the membrane at a high transmission rate, and the battery can maintain a high level of electrical cycle performance.
The carbon coating 1032 coated on the modified diaphragm 1031 is thin, has a thickness of not less than 0.1 μm, has small influence on the transmission rate of lithium ions, and can penetrate through the diaphragm at a high transmission rate; while the carbon coating 1032 directly applied to the initial separator is thick, and the thickness is generally not less than 5 μm, the carbon coating 1032 at the thickness has a large influence on the lithium ion transport rate, so that the lithium ion passing through the separator is low, the unit capacity of the active material is reduced, and the energy density of the battery is reduced.
Further, a carbon coating 1032 is coated on the surface of the modified diaphragm 1031 by suction filtration. Specifically, after the modified membrane 1031 is obtained, the modified membrane 1031 is placed in a constant temperature water bath for wetting treatment, and then the carbon material is uniformly filtered on the surface of the modified membrane 1031 by using a filtering device, so that the uniform coating of the carbon coating 1032 is realized, as detailed in the following embodiments.
In the embodiment of the invention, the thickness of the modified membrane 1031 is 40 μm to 80 μm, the thickness of the carbon coating 1032 is not less than 0.1 μm, the influence of reducing the carbon coating 1032 on the transmission rate of lithium ions is small, and the lithium ions can penetrate through the membrane at a higher transmission rate, so that the energy density of the battery is improved.
Optionally, the carbon coating 1032 comprises a carbon material or a carbon composite comprising the carbon material and an inorganic material, wherein,
the carbon material comprises at least one of acetylene black, ketjen black, carbon nanotubes, graphene and graphene oxide;
the inorganic material comprises at least one of nano-silicon, silicon monoxide, silicon dioxide, tungsten disulfide, molybdenum disulfide and montmorillonite.
The carbon material comprises at least one of acetylene black, ketjen black, carbon nanotubes, graphene and graphene oxide, and a porous structure is formed after the carbon material is coated on the modified diaphragm 1031 and is used for adsorbing polysulfide, so that the shuttle effect of the battery in the electrical cycle process is reduced, and the electrical cycle performance of the battery is improved.
The inorganic material comprises at least one of nano-silicon, silicon monoxide, silicon dioxide, tungsten disulfide, molybdenum disulfide and montmorillonite, and is used for improving the strength of the carbon coating 1032 when the inorganic material is mixed with a carbon material and coated on the modified membrane 1031, so that the carbon coating 1032 can be more tightly coated on the surface of the modified membrane 1031, and the conditions of falling off and the like are avoided.
Further, the carbon coating 1032 needs to include at least a carbon material to improve the electrical cycle performance of the battery; carbon coating 1032 may also include inorganic materials to improve the structural strength of carbon coating 1032 and to prevent carbon coating 1032 from flaking off during electrical cycling.
In an embodiment of the present invention, the carbon coating 1032 comprises a carbon material or a carbon composite material, the carbon composite material comprising a carbon material and an inorganic material, wherein the carbon material comprises at least one of acetylene black, ketjen black, carbon nanotubes, graphene oxide; the inorganic material comprises at least one of nano-silicon, silicon monoxide, silicon dioxide, tungsten disulfide, molybdenum disulfide and montmorillonite, and a porous structure is formed after the modified diaphragm 1031 is coated with a carbon material and is used for adsorbing polysulfide, so that the shuttle effect of the battery in the electrical cycle process is reduced, and the electrical cycle performance of the battery is improved; the structural strength of the carbon coating 1032 is improved by the inorganic material, and the carbon coating 1032 is prevented from falling off in the electrical cycle process.
Optionally, where the carbon coating 1032 includes the carbon composite material, a mass ratio of the inorganic material to the carbon material is 2.5.
It is understood that in the case where the carbon coating 1032 includes a carbon composite material, an excessively high content of the inorganic material results in a less porous structure of the carbon coating 1032, making it difficult to effectively adsorb polysulfides; too low a content of the inorganic material may result in failure of the carbon coating 1032 to be effectively fixed on the surface of the modified membrane 1031, resulting in easy detachment of the carbon coating 1032 from the surface of the membrane. In this embodiment, the mass ratio of the inorganic material to the carbon material is set to 2.5 to 1.
Optionally, the modified diaphragm 1031 is one of a polyethylene diaphragm, a polypropylene diaphragm, or a polyethylene/polypropylene diaphragm mixed diaphragm.
It is understood that the modified membrane 1031 is located between the positive electrode plate 101 and the negative electrode plate 102, and lithium ions need to pass through the modified membrane 1031 for electrical cycling during battery cycling, so the modified membrane 1031 itself needs to have good performance of conducting lithium ions. The modified diaphragm 1031 is one of a polyethylene diaphragm, a polypropylene diaphragm or a polyethylene/polypropylene diaphragm, so that lithium ions can pass through the battery at a high speed during an electrical cycle and the energy density of the battery is maintained at a high level.
Optionally, the volume ratio of alcohol to water is 0.2.
It will be appreciated that prior to ozone polarization of the initial membrane, the membrane may be subjected to ultrasonic treatment in an ultrasonic alcohol-mixed water bath such that the membrane is capable of generating a plurality of hydroxyl and/or carboxyl groups on the surface after ozone polarization. In the embodiment, the volume ratio of alcohol to water is 0.2 to 0.5, so that the surface of the membrane before ozone polarization contains alcohol, and a plurality of hydroxyl groups and/or carboxyl groups can be generated on the surface during ozone polarization, thereby reducing the thickness of the carbon coating 1032 and improving the energy density of the battery.
Optionally, the carbon coating 1032 is obtained by:
mixing the material of the carbon coating 1032 with a binder;
adding a solvent into the mixed mixture, and grinding the mixture until the mixture is dispersed;
adding the dispersed mixture into the solvent for dilution;
carrying out ultrasonic treatment on the diluted mixture;
performing suction filtration on the mixture subjected to ultrasonic treatment on the modified diaphragm 1031 and drying;
wherein the concentration of the diluted mixture is 0.1mg/mL to 1mg/mL.
The adhesive is used to bond the carbon material and the inorganic material in the carbon coating 1032, and the carbon material and the inorganic material after mixing are coated on the surface of the modified membrane 1031, and the carbon coating 1032 can be fixed on the surface of the modified membrane 1031 after drying.
Specifically, the material of the carbon coating 1032 is mixed with a binder, and the mixed mixture is added with a solvent and ground until the mixture is dispersed, wherein the temperature is 20 ℃ to 25 ℃, and the grinding is carried out for 15min to 20min. After milling, the solvent is added continuously for dilution until the mixture is completely dispersed in the solvent.
It is understood that the concentration of the diluted mixture is controlled to be 0.1mg/mL to 1mg/mL, so that when the carbon coating 1032 is suction filtered on the surface of the modified membrane 1031, the thickness of the carbon coating 1032 on the surface of the modified membrane 1031 is controlled to be not less than 1 μm, thereby increasing the rate of lithium ions passing through the membrane and increasing the energy density of the battery.
Further, the diluted solution is attached to the modified membrane 1031 by suction filtration, and then dried at 40 ℃ to 50 ℃ to obtain the modified membrane 1031 coated with the carbon coating 1032. Wherein before the suction filtration, the device is required to be static for 30min to 60min, the suction filtration device is vibrated in the suction filtration process, the vibration frequency is controlled to be 10Hz to 50Hz, the thickness of the carbon coating 1032 can be adjusted by the amount of the solution, and the thickness can be controlled to be at least 0.1 μm.
Optionally, the adhesive includes at least one of polyvinylidene fluoride, polyethylene oxide, polyacrylic acid, and polyvinyl alcohol;
the solvent includes at least one of Dimethylformamide (DMF) or N-methylpyrrolidinone (NMP).
The adhesive is used for bonding and fixing the carbon material and the inorganic material on the surface of the modified diaphragm 1031. The adhesive comprises at least one of polyvinylidene fluoride, polyethylene oxide, polyacrylic acid and polyvinyl alcohol, can be tightly combined with a carbon material and an inorganic material, is coated on the surface of the modified diaphragm 1031, and can be fixed on the surface of the modified diaphragm 1031 after being dried.
The solvent is used for dissolving the carbon material, the inorganic material and the adhesive, so that the carbon material, the inorganic material and the adhesive can be fully dispersed and mixed in the solvent, the mixture is ground in a vacuum environment to obtain a uniform mixture, and the mixture is coated on the surface of the modified diaphragm 1031 and dried. Wherein the solvent comprises dimethylformamide or N-methylpyrrolidone, and the carbon material, the inorganic material and the adhesive are effectively separated by ultrasonic energy; meanwhile, the coating can be volatilized in the drying process after coating, and redundant dimethylformamide or N-methylpyrrolidone is removed.
In the embodiment of the present invention, the adhesive is used to adhere and fix the carbon material and the inorganic material to the surface of the modified diaphragm 1031; the solvent is used for dissolving the carbon material, the inorganic material and the adhesive, so that the carbon material, the inorganic material and the adhesive can be fully dispersed and mixed in the solvent, the mixture is ground in a vacuum environment to obtain a uniform mixture, and the mixture is coated on the surface of the modified diaphragm 1031 and dried. By adding the adhesive and the solvent into the carbon coating 1032, the carbon coating 1032 is coated on the surface of the modified diaphragm 1031, so that the shuttling effect of the battery is reduced, and the energy density of the battery is improved.
Optionally, the electrolyte 20 includes 1,3 dioxolane, ethylene glycol dimethyl ether, lithium bistrifluoromethanesulfonimide, and lithium nitrate, wherein,
the mass ratio of the 1,3 dioxolane to the glyme is 1;
the content of the lithium bistrifluoromethanesulfonylimide is 1mol/L;
the content of the lithium nitrate is 0.2wt%.
The electrolyte 20 is used for transferring lithium ions and completing an electrical cycle, so that the electrolyte 20 has a large amount of lithium ions. In the embodiment, lithium ions are provided by lithium bistrifluoromethanesulfonimide and lithium nitrate, and meanwhile, 1,3 dioxolane and ethylene glycol dimethyl ether are used as solvents and can efficiently transmit the lithium ions, so that the battery has high electrical cycle performance.
Wherein, the mass ratio of 1,3 dioxolane to ethylene glycol dimethyl ether is 1, the content of lithium bistrifluoromethanesulfonimide is 1mol/L, and the content of lithium nitrate is 0.2wt%, so that the electrolyte 20 can rapidly conduct lithium ions while containing more lithium ions, and the battery can be maintained at a higher level of electrical cycle performance.
Referring to fig. 2, fig. 2 is a flow chart of a method for manufacturing a battery according to the present invention, as shown in fig. 2, the method includes:
placing the initial diaphragm in an alcohol mixed water bath for ultrasonic treatment to obtain a first intermediate diaphragm;
placing the first intermediate diaphragm in ultraviolet rays, water vapor and ozone for ultrasonic treatment to obtain a second intermediate diaphragm;
drying the second middle diaphragm to obtain a modified diaphragm;
mixing a carbon material or a carbon composite material with a binder, and adding a solvent for grinding to obtain a ground first mixture;
adding the solvent into the first mixture for dilution to obtain a second mixture;
carrying out suction filtration on the second mixture and the modified diaphragm and drying to obtain a carbon coating coated on the modified diaphragm;
stacking or convolving the positive pole piece, the negative pole piece and the modified diaphragm to obtain a battery core;
and preparing the battery according to the battery core and the electrolyte.
Different examples can be prepared by the above method for comparison to show improvement in cycle performance of the battery. The method comprises the following specific steps:
preparation of the cell of example 1:
placing the initial diaphragm (polypropylene diaphragm) in an ultrasonic alcohol mixed water bath for ultrasonic treatment to obtain a diaphragm A, wherein the ultrasonic time is 40min, and the volume ratio of alcohol to water is controlled to be 0.2:1.
and (3) placing the diaphragm A in an ultraviolet ozone machine for ozone treatment, and simultaneously applying ultrasound in the treatment process to obtain a diaphragm B, wherein the distance between the diaphragm and an ultraviolet lamp is controlled at 5.5cm, the treatment time is 3min, and the ultrasound frequency is 25kHz.
And (3) placing the diaphragm B in a blast drying oven, and drying the diaphragm B in a vertical mode to obtain a modified diaphragm C. The drying temperature is 45 ℃ and the drying time is 30 min.
The preparation method comprises the following steps of ball-milling and mixing acetylene black and ketjen black according to a mass ratio of 2. After complete dispersion, solution a was diluted with NMP to a concentration of 0.5/mL and sonicated for 2h.
And (3) placing the treated diaphragm C in a constant-temperature water/alcohol mixed bath for wetting treatment to obtain a diaphragm D, wherein the volume ratio of water to alcohol is 1:0.05 and a temperature of 45 ℃.
And (3) attaching the diluted solution a to a diaphragm D substrate in a suction filtration mode, and then drying at 40 ℃ to obtain the required modified diaphragm. Wherein before the suction filtration, the device needs to be static for 60min, the suction filtration device is vibrated in a small amplitude in the suction filtration process, and the vibration frequency is controlled at 50Hz.
Cutting the modified membrane into pieces with an area of 1.5cm 2 The corresponding battery of example 1 was assembled in a glove box. The lithium sheet is used as a negative electrode, a common carbon-sulfur mixture is used as a positive electrode, the mass ratio of the electrolyte to the glycol dimethyl ether is 1,3, the mass ratio of dioxolane to glycol dimethyl ether is 1, the content of lithium bistrifluoromethanesulfonimide is 1mol/L, and the content of lithium nitrate is 0.2wt%.
Preparation of the cell of example 2:
placing an initial diaphragm (polyethylene diaphragm) in an ultrasonic alcohol mixed water bath for ultrasonic treatment to obtain a diaphragm A, wherein the ultrasonic time is controlled to be 30-60 min, and the volume ratio of alcohol to water is controlled to be 0.5:1.
and (3) placing the diaphragm A in an ultraviolet ozone machine for ozone treatment, and simultaneously applying ultrasound to obtain a diaphragm B in the treatment process, wherein the distance between the diaphragm and an ultraviolet lamp is controlled at 10cm, the treatment time is 10min, and the ultrasound frequency is 50kHz.
And (3) placing the membrane B in a forced air drying oven, and drying the membrane B vertically to obtain the modified polar membrane C. The drying temperature is 30 ℃, and the drying time is 30 min.
Mixing tungsten disulfide and molybdenum disulfide according to the mass ratio of 3. Grinding at 20 deg.C for 120min, and adding DMF to dilute grinding until completely dispersing. After complete dispersion, solution a was diluted with DMF to a concentration of 1mg/mL and sonicated for 4h.
And (3) placing the treated diaphragm C in a constant-temperature water/alcohol mixed bath for wetting treatment to obtain a diaphragm D, wherein the volume ratio of water to alcohol is controlled to be 1:0.1, controlling the temperature at 60 ℃,
and (3) attaching the diluted solution a to a diaphragm D substrate in a suction filtration mode, and then drying at 50 ℃ to obtain the required modified diaphragm for the lithium-sulfur battery. Wherein before the suction filtration, the device needs to be static for 60min, and the vibration frequency of the device is controlled at 10Hz by vibrating the device with small amplitude in the suction filtration process.
Cutting the modified membrane into pieces with an area of 1.5cm 2 The corresponding cell of example 2 was assembled in a glove box. The lithium sheet is used as a negative electrode, a common carbon-sulfur mixture is used as a positive electrode, the mass ratio of the electrolyte to the glycol dimethyl ether is 1,3, the mass ratio of dioxolane to glycol dimethyl ether is 1, the content of lithium bistrifluoromethanesulfonimide is 1mol/L, and the content of lithium nitrate is 0.2wt%.
A battery of comparative example 1 was prepared:
acetylene black was added to the solvent DMF and designated as solution a. Grinding at 20 deg.C for 120min, and adding DMF to dilute grinding until completely dispersing. After complete dispersion, solution A was diluted with DMF to a concentration of 5mg/mL.
And (3) attaching the diluted solution a to the surface of a common initial diaphragm (a polypropylene diaphragm) in a suction filtration mode, and then drying at 50 ℃ to obtain the required modified diaphragm for the lithium-sulfur battery.
Cutting the modified membrane into pieces with the area of 1.5cm 2 The corresponding cell of comparative example 1 was assembled in a glove box. The lithium sheet is used as a negative electrode, a common carbon-sulfur mixture is used as a positive electrode, the mass ratio of the electrolyte to the glycol dimethyl ether is 1,3, the mass ratio of dioxolane to glycol dimethyl ether is 1, the content of lithium bistrifluoromethanesulfonimide is 1mol/L, and the content of lithium nitrate is 0.2wt%.
The battery of example 1, the battery of example 2, and the battery of comparative example 1 obtained as described above were subjected to a surface infrared test and a discharge test, and the following test results were obtained:
referring to FIG. 3, FIG. 3 is a Fourier infrared image of the surface of the polyethylene separator after treatment in example 2, as seen in FIG. 3 at 3400cm −1 、1634cm −1 、1086cm −1 There are significant alcohol groups (-OH), olefin groups (C = C), and hydroxyl groups (C-OH) due to ozone oxidizing the membrane surface. Alcohol groups and carboxyl groups having electronegativity are broadly classified intoThe lithium ion battery is distributed on the surface of the diaphragm, and in the suction filtration process, the carbon material/inorganic material is uniformly dispersed, the accumulation of particle materials is avoided, the thickness of a suction filtration layer is reduced, the rapid lithium ion transmission capability is ensured, and the energy density of the battery is improved.
Referring to fig. 4, fig. 4 is a battery rate curve obtained in example 2 of the present invention and comparative example 1. As can be seen from FIG. 4, compared with the polypropylene diaphragm prepared by the traditional method, the first-turn capacity of the modified diaphragm can reach 1300mAh/g, and 600mAh/g can be realized on the premise of a high multiplying power of 5C. The modified diaphragm is mainly based on the advantages that the ion conduction capability is strong, no physical gap exists, the polysulfide shuttling effect can be inhibited, the lithium ion transmission is ensured, and the loss of the whole capacity is avoided.
Referring to fig. 5, fig. 5 is a graph of long cycle performance of a battery corresponding to example 1 and a battery corresponding to comparative example 1. As can be seen from fig. 5, the battery prepared by modifying the separator effectively avoids the decrease of the battery capacity, and ensures the stability of the overall capacity. It can be found from experimental data that the battery capacity obtained in example 1 can obtain an appreciable unit capacity of 1000mAh/g (comparative example 1 is only 990 mAh/g), and in particular, the modified separator still maintains a unit capacity of 600mAh/g after 200 cycles, which is much higher than 500mAh/g of comparative example 1. The coating thickness can achieve 5.4 mu m, the coating can be ensured to be uniform and complete, the normal transmission of lithium ions is not influenced, polysulfide can be effectively adsorbed, the shuttle of polysulfide is blocked, and the capacity and the cycle performance of the lithium-sulfur battery are improved.
In conclusion, it can be confirmed that the battery made of the modified diaphragm obtained by the embodiment of the invention has better lithium ion transport capability, and further the energy density of the battery is improved.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a component of' 8230; \8230;" does not exclude the presence of another like element in a process, method, article, or apparatus that comprises the element.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A battery is characterized by comprising a battery core and electrolyte, wherein the battery core comprises a positive pole piece, a negative pole piece and a modified diaphragm which are stacked or wound, and the modified diaphragm is positioned between the positive pole piece and the negative pole piece,
the surface of the modified diaphragm is coated with a carbon coating, and the surface of the modified diaphragm is provided with a plurality of hydroxyl groups and/or a plurality of carboxyl groups;
the modified membrane is obtained by the following steps:
placing the initial diaphragm in an alcohol mixed water bath for first ultrasonic treatment;
placing the diaphragm subjected to the first ultrasonic treatment in ultraviolet rays, water vapor and ozone for second ultrasonic treatment;
and drying the diaphragm subjected to the second ultrasonic treatment.
2. The battery of claim 1, wherein the carbon coating has a thickness of not less than 0.1 μm.
3. The battery of claim 1, wherein the carbon coating comprises a carbon material or a carbon composite comprising the carbon material and an inorganic material, wherein,
the carbon material comprises at least one of acetylene black, ketjen black, carbon nanotubes, graphene and graphene oxide;
the inorganic material comprises at least one of nano-silicon, silicon monoxide, silicon dioxide, tungsten disulfide, molybdenum disulfide and montmorillonite.
4. The battery according to claim 3, wherein in a case where the carbon coating layer includes the carbon composite material, a mass ratio of an inorganic material to the carbon material is 2.5 to 3.
5. The battery of claim 1, wherein the modified separator is one of a polyethylene separator, a polypropylene separator, or a polyethylene/polypropylene separator hybrid separator.
6. The battery of claim 1, wherein the volume ratio of alcohol to water is 0.2.
7. The battery according to any one of claims 1 to 6, wherein the carbon coating is obtained by:
mixing the material of the carbon coating with a binder;
adding a solvent into the mixed mixture, and grinding the mixture until the mixture is dispersed;
adding the dispersed mixture into the solvent for dilution;
carrying out ultrasonic treatment on the diluted mixture;
filtering the mixture subjected to ultrasonic treatment on the modified diaphragm, and drying;
wherein the concentration of the diluted mixture is 0.1mg/mL to 1mg/mL.
8. The battery of claim 7, wherein the binder comprises at least one of polyvinylidene fluoride, polyethylene oxide, polyacrylic acid, polyvinyl alcohol;
the solvent includes at least one of dimethylformamide or N-methylpyrrolidone.
9. The cell of any one of claims 1 to 6, wherein the electrolyte comprises 1,3 dioxolane, ethylene glycol dimethyl ether, lithium bistrifluoromethanesulfonimide, and lithium nitrate, wherein,
the mass ratio of the 1,3 dioxolane to the glyme is 1;
the content of the lithium bis (trifluoromethanesulfonyl) imide is 1mol/L;
the content of the lithium nitrate is 0.2wt%.
10. A method of making a battery, comprising:
placing the initial diaphragm in an alcohol mixed water bath for ultrasonic treatment to obtain a first intermediate diaphragm;
placing the first intermediate diaphragm in ultraviolet rays, water vapor and ozone for ultrasonic treatment to obtain a second intermediate diaphragm;
drying the second middle diaphragm to obtain a modified diaphragm;
mixing a carbon material or a carbon composite material with a binder, and adding a solvent for grinding to obtain a ground first mixture;
adding the solvent into the first mixture for dilution to obtain a second mixture;
carrying out suction filtration and drying on the second mixture and the modified diaphragm to obtain a carbon coating coated on the modified diaphragm;
stacking or convolving the positive pole piece, the negative pole piece and the modified diaphragm to obtain a battery core;
and preparing the battery according to the battery core and the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310244134.7A CN115939671A (en) | 2023-03-15 | 2023-03-15 | Battery and battery preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310244134.7A CN115939671A (en) | 2023-03-15 | 2023-03-15 | Battery and battery preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115939671A true CN115939671A (en) | 2023-04-07 |
Family
ID=86701006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310244134.7A Pending CN115939671A (en) | 2023-03-15 | 2023-03-15 | Battery and battery preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115939671A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01310523A (en) * | 1988-06-09 | 1989-12-14 | Matsushita Electric Ind Co Ltd | Electric double-layer capacitor |
| CN105633471A (en) * | 2014-11-04 | 2016-06-01 | 中国电子科技集团公司第十八研究所 | Preparation method of carbon-coated membrane lithium-sulfur battery |
| CN106960933A (en) * | 2015-12-02 | 2017-07-18 | Sk新技术株式会社 | Heat resistance and the excellent secondary cell barrier film of closing property |
| CN108172739A (en) * | 2017-12-22 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | The carboxylated diaphragm and preparation method of the additional Iy self-assembled layer of lithium-sulfur cell |
| CN108461694A (en) * | 2018-04-24 | 2018-08-28 | 清华大学 | A kind of economic benefits and social benefits composite diaphragm of lithium-sulfur cell and preparation method thereof |
| CN112531281A (en) * | 2020-09-25 | 2021-03-19 | 山东大学 | Preparation method of modified diaphragm for lithium-sulfur battery based on nano metal hydroxide-carbon composite material |
| CN113013549A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm |
| CN114361714A (en) * | 2021-12-06 | 2022-04-15 | 惠州市旭然新能源有限公司 | Coating slurry, preparation method thereof, composite porous diaphragm prepared from coating slurry and lithium ion battery |
-
2023
- 2023-03-15 CN CN202310244134.7A patent/CN115939671A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01310523A (en) * | 1988-06-09 | 1989-12-14 | Matsushita Electric Ind Co Ltd | Electric double-layer capacitor |
| CN105633471A (en) * | 2014-11-04 | 2016-06-01 | 中国电子科技集团公司第十八研究所 | Preparation method of carbon-coated membrane lithium-sulfur battery |
| CN106960933A (en) * | 2015-12-02 | 2017-07-18 | Sk新技术株式会社 | Heat resistance and the excellent secondary cell barrier film of closing property |
| CN108172739A (en) * | 2017-12-22 | 2018-06-15 | 哈尔滨工业大学深圳研究生院 | The carboxylated diaphragm and preparation method of the additional Iy self-assembled layer of lithium-sulfur cell |
| CN108461694A (en) * | 2018-04-24 | 2018-08-28 | 清华大学 | A kind of economic benefits and social benefits composite diaphragm of lithium-sulfur cell and preparation method thereof |
| CN112531281A (en) * | 2020-09-25 | 2021-03-19 | 山东大学 | Preparation method of modified diaphragm for lithium-sulfur battery based on nano metal hydroxide-carbon composite material |
| CN113013549A (en) * | 2021-01-28 | 2021-06-22 | 清华大学 | Coating material for light-weight lithium ion battery diaphragm, preparation method of coating material and light-weight lithium ion battery composite diaphragm |
| CN114361714A (en) * | 2021-12-06 | 2022-04-15 | 惠州市旭然新能源有限公司 | Coating slurry, preparation method thereof, composite porous diaphragm prepared from coating slurry and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20200411863A1 (en) | Lithium-sulfur battery cathode material and preparation method thereof, lithium-sulfur battery cathode and preparation method thereof, and lithium-sulfur battery | |
| CN111725468B (en) | Silicon dioxide inorganic nanoparticle reinforced polyolefin diaphragm and application thereof | |
| CN111916640B (en) | WS2/CNTs modified diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN106711430A (en) | Production method of lithium/carbon fiber or porous carbon paper/copper foil composite negative electrode used for lithium-sulfur battery | |
| CN111564639B (en) | Lithium ion battery pole piece, preparation method and application thereof | |
| CN111370626A (en) | Synergistic mechanism lithium-sulfur diaphragm, preparation method thereof and lithium-sulfur battery | |
| CN111540868A (en) | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm | |
| CN112635712A (en) | Negative plate and lithium ion battery | |
| CN114242943A (en) | Graphene film and preparation method thereof, symmetrical battery and preparation method thereof, full battery and preparation method thereof | |
| CN116207338A (en) | Solid electrolyte membrane, preparation method and application thereof, and solid battery | |
| CN103227329A (en) | Positive electrode, method of manufacturing the same, and lithium battery comprising the positive electrode | |
| CN114069037A (en) | Gel polymer electrolyte, preparation method and application thereof, solid-state lithium battery and preparation method thereof | |
| CN116169302A (en) | Negative electrode current collector, negative electrode plate and battery comprising negative electrode plate | |
| WO2024183499A1 (en) | Negative electrode material, negative electrode sheet and battery | |
| CN114400297A (en) | Lithium ion battery composite pole piece containing aerogel coating and preparation method thereof | |
| CN113629353A (en) | PET (polyethylene terephthalate) basic weight ion track composite diaphragm for lithium ion battery and preparation method of PET basic weight ion track composite diaphragm | |
| KR101657742B1 (en) | Positive electrode for secondary battery and the method for manufacturing the same | |
| CN116154169B (en) | MXene coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery | |
| CN114188664B (en) | Lithium supplement isolating membrane and preparation method thereof, and battery cell containing lithium supplement isolating membrane and preparation method thereof | |
| CN115939671A (en) | Battery and battery preparation method | |
| CN114614200A (en) | Electrochemical device and electric equipment | |
| CN114864872A (en) | Composite electrode and preparation method and application thereof | |
| CN115051108A (en) | Battery diaphragm coating slurry containing sodium methyl silicate, battery diaphragm, battery and preparation method of battery | |
| CN113629354A (en) | Lithium ion battery diaphragm suitable for liquid electrolyte based on heavy ion track membrane and preparation method thereof | |
| CN114583094A (en) | Lithium ion battery capable of improving low-temperature performance and preparation method thereof |
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: 20230407 |