CN116314624A - Preparation method of miniature flexible lithium ion battery based on carbon aerogel - Google Patents
Preparation method of miniature flexible lithium ion battery based on carbon aerogel Download PDFInfo
- Publication number
- CN116314624A CN116314624A CN202310266285.2A CN202310266285A CN116314624A CN 116314624 A CN116314624 A CN 116314624A CN 202310266285 A CN202310266285 A CN 202310266285A CN 116314624 A CN116314624 A CN 116314624A
- Authority
- CN
- China
- Prior art keywords
- battery
- positive electrode
- aerogel
- carbon aerogel
- negative electrode
- 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
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002033 PVDF binder Substances 0.000 claims abstract description 43
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 43
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011267 electrode slurry Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011889 copper foil Substances 0.000 claims abstract description 14
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006230 acetylene black Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000005538 encapsulation Methods 0.000 claims abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 48
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 27
- 239000004964 aerogel Substances 0.000 claims description 20
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000002985 plastic film Substances 0.000 claims description 16
- 229920006255 plastic film Polymers 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000011240 wet gel Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 28
- 238000002156 mixing Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000010000 carbonizing Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/023—Gel electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a miniature flexible lithium ion battery based on carbon aerogel, belongs to the technical field of lithium ion batteries, and solves the technical problem of the miniature requirement of the flexible battery in the prior art. The method comprises the following steps: uniformly grinding lithium manganate, acetylene black and polyvinylidene fluoride, dissolving the mixture in a 1-methyl-2-pyrrolidone solution to prepare positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and drying the aluminum foil to obtain a positive electrode plate; uniformly grinding carbon aerogel and polyvinylidene fluoride, dissolving the carbon aerogel and polyvinylidene fluoride in a 1-methyl-2-pyrrolidone solution to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode plate; the positive electrode plate, the diaphragm and the negative electrode plate are sequentially stacked to prepare a battery main body; the battery main body is arranged in the flexible battery shell, and electrolyte is added into the battery main body to complete the encapsulation of the flexible lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a miniature flexible lithium ion battery based on carbon aerogel.
Background
With the advent of various deformable mobile electronic devices, deformable flexible energy storage devices have received widespread attention for powering them. At present, more flexible energy storage devices are researched as flexible super capacitors, but the low energy density severely limits the practical application scenarios. The flexible lithium ion battery not only has the advantage of high energy density, but also has the advantages of high working voltage, small volume, light weight, high energy, no memory effect, no pollution, small self discharge, long cycle life and the like, and is an ideal energy storage device for the development of the 21 st century. However, the conventional cylindrical or square full battery takes stainless steel material as a battery shell, and the requirement of current flexible deformation cannot be obviously met, so that the preparation of the soft-packed battery becomes a necessary requirement for preparing the flexible lithium ion battery.
In addition, with the increasing popularity of wearable electronic products, requirements for light weight, miniaturization and the like are also put forward for the flexible energy storage device. Electrode materials are an important component of flexible energy storage devices, and solid-aerogel with minimum density in the world attracts wide attention in view of the current demand for light weight. The carbon aerogel is a novel nano porous carbon material with a cross-linked structure, which is generated by solid-phase carbonization reaction of organic aerogel, and is the only aerogel with conductivity and chemical stability. The density variation range is wide, the structure is adjustable, the porosity reaches 80% -99.8%, the pore diameter is generally less than 50nm, the specific surface area is as high as 400-3000 m < 2 >/g, and the comprehensive performance is superior to that of the traditional carbon materials such as graphite. The material with the special structure has wide application prospect, and particularly has excellent performance when being used as an electrode material in electrochemistry.
In summary, the micro soft-package flexible lithium ion battery using the carbon aerogel as the negative electrode material is prepared, so that the requirement of the current electronic product on the miniaturized flexible battery energy storage device is well met, and the micro soft-package flexible lithium ion battery has a profound practical application value.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon aerogel-based miniature flexible lithium ion battery, which solves the technical problem of the miniaturization requirement of the flexible battery in the prior art.
The invention provides a preparation method of a miniature flexible lithium ion battery based on carbon aerogel, which comprises the following steps: uniformly grinding lithium manganate, acetylene black and polyvinylidene fluoride, dissolving the mixture in a 1-methyl-2-pyrrolidone solution to prepare positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and drying the aluminum foil to obtain a positive electrode plate;
uniformly grinding carbon aerogel and polyvinylidene fluoride, dissolving the carbon aerogel and polyvinylidene fluoride in a 1-methyl-2-pyrrolidone solution to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode plate;
the positive electrode plate, the diaphragm and the negative electrode plate are sequentially stacked to prepare a battery main body;
the battery main body is arranged in the flexible battery shell, and electrolyte is added into the battery main body to complete the encapsulation of the flexible lithium ion battery.
Further, in the step of uniformly grinding lithium manganate, acetylene black and polyvinylidene fluoride, dissolving the mixture in a 1-methyl-2-pyrrolidone solution to prepare positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and drying the aluminum foil to obtain a positive electrode plate, the mass ratio of the lithium manganate, the acetylene black and the polyvinylidene fluoride is 8:1:1.
further, in the step of uniformly grinding the carbon aerogel and the polyvinylidene fluoride, dissolving the carbon aerogel and the polyvinylidene fluoride in a 1-methyl-2-pyrrolidone solution to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode plate, the mass ratio of the carbon aerogel to the polyvinylidene fluoride is 9:1.
further, in the step of sequentially stacking the positive electrode plate, the diaphragm and the negative electrode plate to prepare the battery main body, the diaphragm is a microporous diaphragm.
Further, the battery body is arranged in the flexible battery shell, and electrolyte is added into the battery body to complete the packaging of the flexible lithium ion battery,
the battery shell is an aluminum plastic film;
the electrolyte is lithium hexafluorophosphate electrolyte which is dissolved in a mixed organic solvent of ethyl cellulose and ethyl mercury chloride, wherein the volume ratio of the ethyl cellulose to the ethyl mercury chloride is 1:1.
further, the battery main body is arranged in the flexible battery shell, and electrolyte is added into the battery main body, so that the packaging process of the flexible lithium ion battery is performed in a glove box under the protection of fully-closed argon.
In a second aspect, the present invention also provides a method for preparing a carbon aerogel, comprising:
resorcinol and formaldehyde are used as precursors, sodium carbonate is used as a catalyst, water is used as a solvent, and RF organic wet gel is obtained through sol-gel, aging and solvent replacement;
obtaining RF aerogel after normal pressure drying process;
and (3) performing high-temperature carbonization and gas activation treatment on the RF aerogel to obtain the nano porous carbon aerogel.
Further, in the step of obtaining the RF aerogel after sol-gel, aging, solvent replacement and normal pressure drying process by taking resorcinol and formaldehyde as precursors, sodium carbonate as a catalyst and water as a solvent,
the molar ratio of resorcinol to formaldehyde is 1:2;
the concentration of sodium carbonate was 0.05mol/L.
Further, the sol was aged for 72 hours at 80 ℃.
Further, in the step of preparing the nano porous carbon aerogel by high-temperature carbonization and gas activation treatment of the RF aerogel,
the high-temperature carbonization time of the RF aerogel is 4 hours, and the carbonization temperature is 1050 ℃;
the time for the activation of the RF aerogel gas was 4 hours and the carbonization temperature was 1050 ℃.
The preparation method of the carbon aerogel-based miniature flexible lithium ion battery provided by the invention comprises a flexible battery shell and a battery main body, wherein the flexible battery shell adopts an aluminum plastic film as a packaging material, the battery main body consists of a positive electrode plate, a diaphragm and a negative electrode plate, the positive electrode plate adopts lithium manganate as an active substance, the negative electrode plate adopts carbon aerogel with different proportions as an active substance, the whole preparation and test process is simple and easy to implement, the safety and the high efficiency are realized, and the electrochemical test result shows that the flexible lithium ion battery effectively overcomes a plurality of defects of the traditional button battery and has a wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a carbon aerogel sample prepared according to an embodiment of the present invention, at 10000 times;
fig. 2 is a schematic diagram of a lithium ion flexible battery prepared according to an embodiment of the present invention;
fig. 3 is a constant current charge-discharge curve chart of the lithium ion flexible battery prepared according to the embodiment of the invention;
the drawings show that the battery comprises a 1-aluminum tab, a 2-nickel tab and a 3-battery shell.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terms "comprising" and "having" and any variations thereof, as used in the embodiments of the present invention, are intended to cover non-exclusive inclusion. For example, a process, method, system, article, or apparatus that comprises a list of steps or elements is not limited to only those listed but may optionally include other steps or elements not listed or inherent to such process, method, article, or apparatus.
A preparation method of a miniature flexible lithium ion battery based on carbon aerogel comprises the following steps:
and S1, uniformly mixing active substances lithium manganate, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF), dissolving the mixture into a 1-methyl-2-pyrrolidone solution to form electrode slurry, uniformly coating the electrode slurry on an aluminum foil, and drying the electrode slurry to obtain the positive electrode plate.
Step S2: uniformly mixing active substance carbon aerogel and binder polyvinylidene fluoride (PVDF) and dissolving the mixture into 1-methyl-2-pyrrolidone solution to form electrode slurry, uniformly coating the electrode slurry on copper foil, and drying to obtain the negative electrode plate.
Step S3: aluminum lugs are respectively connected to the positive electrode plates, and nickel lugs are connected to the negative electrode plates. And the positive electrode plate and the diaphragm (Celgard 2500 in the United states) are sequentially stacked to prepare a battery main body.
Step S4: and placing the battery main body in a flexible battery shell, and adding electrolyte into the battery shell in a glove box protected by fully-closed argon to complete packaging.
A method of making a carbon aerogel comprising:
step A1: resorcinol, formaldehyde and sodium carbonate are fully dissolved in deionized water, packaged in a weighing bottle, and subjected to gel aging treatment at 80 ℃ for 72 hours to obtain the RF organic wet gel.
Step A2: and replacing water in the gel with acetone for three times at normal pressure and room temperature, and once every 24 hours, and obtaining the RF organic aerogel after the acetone is naturally volatilized completely.
Step A3: carbonizing for 4 hours at a high temperature of 1050 ℃ in a protective atmosphere of nitrogen, and then obtaining the light porous carbon aerogel material required by the preparation of the electrode by a carbon dioxide gas activation technology at 1050 ℃.
In the case of example 1,
the step S1 specifically comprises the steps of taking resorcinol and formaldehyde as reactants, mixing resorcinol and formaldehyde in a molar ratio of 1:2, and taking sodium carbonate solution with a concentration of 0.05mol/L as a catalyst; the molar ratio of resorcinol to sodium carbonate is 1500; deionized water is used as a solvent, the mass fraction of the solution is 30 percent, the solution is stirred uniformly, and the solution is placed in an oven for treatment at 80 ℃ for 72 hours after being sealed, so that the RF organic wet gel is generated.
The samples were immersed in acetone for a solvent replacement of 72 hours, during which the acetone was replaced every 24 hours. And after the acetone is naturally volatilized completely, obtaining the RF organic aerogel. And carbonizing under the protection of nitrogen according to a certain carbonization curve to obtain the carbon aerogel (CRF) with the three-dimensional pore structure.
The step S2 specifically comprises grinding the carbon aerogel obtained by high-temperature carbonization into powder, filtering by using a 200-mesh sieve, mixing the carbon aerogel powder and polyvinylidene fluoride (PVDF) according to a certain proportion (CRF: PVDF=9:1), adding a solvent of 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on the copper foil. Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated copper foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting nickel plate lugs on the negative electrode plates.
The step S3 specifically comprises the steps of mixing commercial lithium manganate, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding solvent 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on aluminum foil. Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated aluminum foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting aluminum sheet lugs on the positive electrode plates.
Step S4 specifically comprises stacking a cut positive electrode plate, a diaphragm (Celgard 2500) and a negative electrode plate in sequence to form a battery main body, then placing the battery main body in an aluminum plastic film, sealing three sides of an aluminum plastic film shell by a packaging machine, finally placing the aluminum plastic film in a glove box (German Unilab, keeping the water and oxygen content in the glove box to be less than 1 ppm), injecting 1mol/L LiPF6 electrolyte (LiPF 6 is dissolved in an organic solvent, the organic solvent is EC: EMC=1:1, wherein the volume ratio is 1:1), sealing the surface to complete the assembly of the flexible lithium ion battery, and finally performing electrochemical test.
In the case of example 2,
the step S1 specifically comprises the steps of taking resorcinol and formaldehyde as reactants, mixing resorcinol and formaldehyde in a molar ratio of 1:2, taking a sodium carbonate solution with a molar ratio of 0.05mol/L as a catalyst, taking resorcinol and sodium carbonate as 1500, taking deionized water as a solvent, uniformly stirring the solution with a mass fraction of 40%, sealing the solution, placing the solution in an oven, and treating the solution at 80 ℃ for 72 hours to finally generate the RF organic wet gel.
The samples were immersed in acetone for a solvent replacement of 72 hours, during which the acetone was replaced every 24 hours. And after the acetone is naturally volatilized completely, obtaining the RF organic aerogel.
Carbonizing under nitrogen protection according to a certain carbonization curve to obtain carbon aerogel (CRF) with a three-dimensional pore structure;
the step S2 specifically comprises grinding the carbon aerogel obtained by high-temperature carbonization into powder, filtering by using a 200-mesh sieve, mixing the carbon aerogel powder and polyvinylidene fluoride (PVDF) according to a certain proportion (CRF: PVDF=9:1), adding a solvent of 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on the copper foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated copper foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting nickel plate lugs on the negative electrode plates.
The step S3 specifically comprises the steps of mixing commercial lithium manganate, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding solvent 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on aluminum foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated aluminum foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting aluminum sheet lugs on the positive electrode plates.
Step S4 specifically comprises stacking a cut positive electrode plate, a diaphragm (Celgard 2500) and a negative electrode plate in sequence to form a battery main body, then placing the battery main body in an aluminum plastic film, sealing three sides of an aluminum plastic film shell by a packaging machine, finally placing the aluminum plastic film in a glove box (German Unilab, keeping the water and oxygen content in the glove box to be less than 1 ppm), injecting 1mol/L LiPF6 electrolyte (LiPF 6 is dissolved in an organic solvent, the organic solvent is EC: EMC=1:1, wherein the volume ratio is 1:1), sealing the surface to complete the assembly of the flexible lithium ion battery, and finally performing electrochemical test.
In the case of example 3,
the step S1 specifically comprises the steps of taking resorcinol and formaldehyde as reactants, mixing resorcinol and formaldehyde in a molar ratio of 1:2, taking a sodium carbonate solution with a molar ratio of 0.05mol/L as a catalyst, taking deionized water as a solvent, taking resorcinol and sodium carbonate as a solvent, uniformly stirring the solution with a mass fraction of 30%, sealing the solution, placing the solution in an oven, and treating the solution at 80 ℃ for 72 hours to finally generate the RF organic wet gel.
The samples were immersed in acetone for a solvent replacement of 72 hours, during which the acetone was replaced every 24 hours. And after the acetone is naturally volatilized completely, obtaining the RF organic aerogel.
And carbonizing under the protection of nitrogen according to a certain carbonization curve to obtain the carbon aerogel (CRF) with the three-dimensional pore structure.
The step S2 specifically comprises grinding the carbon aerogel obtained by high-temperature carbonization into powder, filtering by using a 200-mesh sieve, mixing the carbon aerogel powder and polyvinylidene fluoride (PVDF) according to a certain proportion (CRF: PVDF=9:1), adding a solvent of 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on the copper foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated copper foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting nickel plate lugs on the negative electrode plates.
The step S3 specifically comprises the steps of mixing commercial lithium manganate, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding solvent 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on aluminum foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated aluminum foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting aluminum sheet lugs on the positive electrode plates;
step S4 specifically comprises stacking a cut positive electrode plate, a diaphragm (Celgard 2500) and a negative electrode plate in sequence to form a battery main body, then placing the battery main body in an aluminum plastic film, sealing three sides of an aluminum plastic film shell by a packaging machine, finally placing the aluminum plastic film in a glove box (German Unilab, keeping the water and oxygen content in the glove box to be less than 1 ppm), injecting 1mol/L LiPF6 electrolyte (LiPF 6 is dissolved in an organic solvent, the organic solvent is EC: EMC=1:1, wherein the volume ratio is 1:1), sealing the surface to complete the assembly of the flexible lithium ion battery, and finally performing electrochemical test.
In the case of example 4,
the step S1 specifically comprises the steps of taking resorcinol and formaldehyde as reactants, mixing resorcinol and formaldehyde in a molar ratio of 1:2, taking a sodium carbonate solution with a molar ratio of 0.05mol/L as a catalyst, taking deionized water as a solvent, taking resorcinol and sodium carbonate as a solvent, taking the mass fraction of the solution as 30%, uniformly stirring, sealing, placing in an oven, and treating at 80 ℃ for 72 hours to finally generate the RF organic wet gel.
The samples were immersed in acetone for a solvent replacement of 72 hours, during which the acetone was replaced every 24 hours. And after the acetone is naturally volatilized completely, obtaining the RF organic aerogel.
And carbonizing under nitrogen protection according to a certain carbonization curve, and carbonizing under nitrogen protection to obtain the carbon aerogel (CRF) with the three-dimensional pore structure.
The step S2 specifically comprises grinding the carbon aerogel obtained by high-temperature carbonization into powder, filtering by using a 200-mesh sieve, mixing the carbon aerogel powder and polyvinylidene fluoride (PVDF) according to a certain proportion (CRF: PVDF=9:1), adding a solvent of 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on the copper foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated copper foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting nickel plate lugs on the negative electrode plates.
The step S3 specifically comprises the steps of mixing commercial lithium manganate, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding solvent 1-methyl-2-pyrrolidone to adjust to a certain viscosity, and uniformly coating on aluminum foil.
Naturally drying at room temperature, and vacuum drying at 80deg.C for 12 hr. Cutting the coated aluminum foil into electrode plates with the area of 3cm multiplied by 5cm, and connecting aluminum sheet lugs on the positive electrode plates.
Step S4 specifically comprises stacking a cut positive electrode plate, a diaphragm (Celgard 2500) and a negative electrode plate in sequence to form a battery main body, then placing the battery main body in an aluminum plastic film, sealing three sides of an aluminum plastic film shell by a packaging machine, finally placing the aluminum plastic film in a glove box (German Unilab, keeping the water and oxygen content in the glove box to be less than 1 ppm), injecting 1mol/L LiPF6 electrolyte (LiPF 6 is dissolved in an organic solvent, the organic solvent is EC: EMC=1:1, wherein the volume ratio is 1:1), sealing the surface to complete the assembly of the flexible lithium ion battery, and finally performing electrochemical test.
Embodiments 1 to 4 can achieve the following technical effects:
1. the invention adopts the high-performance light carbon aerogel material as the negative electrode active material, thereby meeting the current requirements on the light flexible energy storage device; the high-performance electrode material promotes the high integration of the electronic device and meets the miniaturization requirement of the flexible energy storage device.
2. Resorcinol and formaldehyde are used as precursor reactants, sodium carbonate solution is used as a catalyst, and an organic wet gel is prepared by a sol-gel method; the solvent is replaced, the conventional supercritical drying technology is replaced by the normal pressure drying technology, and the method is simple and feasible, and reduces experimental risks and cost; the specific surface area and the pore rate of the carbon aerogel are greatly improved by adopting a carbon dioxide gas activation technology.
3. According to the invention, carbon aerogel powder is used as a negative electrode active material, lithium manganate is used as a positive electrode active material, an aluminum plastic film is used as a battery shell, electrolyte is added into a glove box under the protection of fully-closed argon, and a lithium ion soft-packed battery is packaged.
The invention has low environmental requirements from the preparation of the active material in the early stage to the assembly and forming of the soft package battery in the later stage, and the whole process is simple and easy to implement.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the present invention, it should be noted that, directions or positional relationships indicated by terms such as "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., are directions or positional relationships based on those shown in the drawings, or are directions or positional relationships conventionally put in use of the inventive product, are merely for convenience of describing the present invention and simplifying the description, and are not indicative or implying that the apparatus or element to be referred to must have a specific direction, be constructed and operated in a specific direction, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," "third," and the like are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
In the description of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
The device provided by the embodiment of the invention can be specific hardware on the equipment or software or firmware installed on the equipment. The device provided by the embodiment of the present invention has the same implementation principle and technical effects as those of the foregoing method embodiment, and for the sake of brevity, reference may be made to the corresponding content in the foregoing method embodiment where the device embodiment is not mentioned. It will be clear to those skilled in the art that, for convenience and brevity, the specific operation of the system, apparatus and unit described above may refer to the corresponding process in the above method embodiment, which is not described in detail herein.
In the several embodiments provided in the present invention, it should be understood that the disclosed apparatus and method may be implemented in other manners. The apparatus embodiments described above are merely illustrative, for example, of the flowcharts and block diagrams in the figures that illustrate the architecture, functionality, and operation of possible implementations of apparatus, methods and computer program products according to various embodiments of the present invention. In this regard, each block in the flowchart or block diagrams may represent a module, segment, or portion of code, which comprises one or more executable instructions for implementing the specified logical function(s). It should also be noted that in some alternative implementations, the functions noted in the block may occur out of the order noted in the figures. For example, two blocks shown in succession may, in fact, be executed substantially concurrently, or the blocks may sometimes be executed in the reverse order, depending upon the functionality involved. It will also be noted that each block of the block diagrams and/or flowchart illustration, and combinations of blocks in the block diagrams and/or flowchart illustration, can be implemented by special purpose hardware-based systems which perform the specified functions or acts, or combinations of special purpose hardware and computer instructions.
Finally, it should be noted that: the above examples are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, but it should be understood by those skilled in the art that the present invention is not limited thereto, and that the present invention is described in detail with reference to the foregoing examples: any person skilled in the art may modify or easily conceive of the technical solution described in the foregoing embodiments, or perform equivalent substitution of some of the technical features, while remaining within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit of the corresponding technical solutions. Are intended to be encompassed within the scope of the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the carbon aerogel-based miniature flexible lithium ion battery is characterized by comprising the following steps of:
uniformly grinding lithium manganate, acetylene black and polyvinylidene fluoride, dissolving the mixture in a 1-methyl-2-pyrrolidone solution to prepare positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and drying the aluminum foil to obtain a positive electrode plate;
uniformly grinding carbon aerogel and polyvinylidene fluoride, dissolving the carbon aerogel and polyvinylidene fluoride in a 1-methyl-2-pyrrolidone solution to prepare negative electrode slurry, uniformly coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode plate;
the positive electrode plate, the diaphragm and the negative electrode plate are sequentially stacked to prepare a battery main body;
the battery main body is arranged in the flexible battery shell, and electrolyte is added into the battery main body to complete the encapsulation of the flexible lithium ion battery.
2. The method of claim 1, wherein in the step of uniformly grinding lithium manganate, acetylene black and polyvinylidene fluoride, dissolving the mixture in a 1-methyl-2-pyrrolidone solution to prepare positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil, and drying the positive electrode slurry to obtain a positive electrode plate, the mass ratio of the lithium manganate, the acetylene black and the polyvinylidene fluoride is 8:1:1.
3. the method according to claim 2, wherein in the step of uniformly grinding the carbon aerogel and the polyvinylidene fluoride, dissolving the carbon aerogel and the polyvinylidene fluoride in a 1-methyl-2-pyrrolidone solution to prepare a negative electrode slurry, uniformly coating the negative electrode slurry on a copper foil, and drying to obtain a negative electrode sheet, the mass ratio of the carbon aerogel to the polyvinylidene fluoride is 9:1.
4. the method according to claim 3, wherein in the step of manufacturing the battery body by sequentially stacking the positive electrode tab, the separator and the negative electrode tab, the separator is a microporous separator.
5. The method of claim 4, wherein the battery body is disposed within a flexible battery housing and an electrolyte is added thereto to complete the packaging of the flexible lithium ion battery,
the battery shell is an aluminum plastic film;
the electrolyte is lithium hexafluorophosphate electrolyte which is dissolved in a mixed organic solvent of ethyl cellulose and ethyl mercury chloride, wherein the volume ratio of the ethyl cellulose to the ethyl mercury chloride is 1:1.
6. the method of claim 5, wherein the battery body is placed in a flexible battery case, and an electrolyte is added thereto, and the packaging of the flexible lithium ion battery is performed in a glove box under the protection of fully-enclosed argon.
7. A method for preparing a carbon aerogel for use in the method of any one of claims 1-6, comprising:
resorcinol and formaldehyde are used as precursors, sodium carbonate is used as a catalyst, water is used as a solvent, and RF organic wet gel is obtained through sol-gel, aging and solvent replacement;
obtaining RF aerogel after normal pressure drying process;
and (3) performing high-temperature carbonization and gas activation treatment on the RF aerogel to obtain the nano porous carbon aerogel.
8. The method of claim 7, wherein in the steps of obtaining RF aerogel by sol-gel, aging, solvent replacement, and normal pressure drying with resorcinol and formaldehyde as precursors and sodium carbonate as catalyst and water as solvent,
the molar ratio of resorcinol to formaldehyde is 1:2;
the concentration of sodium carbonate was 0.05mol/L.
9. The method of claim 8, wherein the sol is aged for 72 hours at 80 ℃.
10. The method of claim 7, wherein the RF aerogel is carbonized at high temperature and gas activated to obtain the nano-porous carbon aerogel,
the high-temperature carbonization time of the RF aerogel is 4 hours, and the carbonization temperature is 1050 ℃;
the time for the activation of the RF aerogel gas was 4 hours and the carbonization temperature was 1050 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310266285.2A CN116314624A (en) | 2023-03-17 | 2023-03-17 | Preparation method of miniature flexible lithium ion battery based on carbon aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310266285.2A CN116314624A (en) | 2023-03-17 | 2023-03-17 | Preparation method of miniature flexible lithium ion battery based on carbon aerogel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116314624A true CN116314624A (en) | 2023-06-23 |
Family
ID=86833874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310266285.2A Pending CN116314624A (en) | 2023-03-17 | 2023-03-17 | Preparation method of miniature flexible lithium ion battery based on carbon aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116314624A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376498A (en) * | 2008-10-07 | 2009-03-04 | 同济大学 | Carbon aerogel and preparation of lithium ion button shape cell with the carbon aerogel as cathode |
| CN201294156Y (en) * | 2008-09-12 | 2009-08-19 | 东莞市迈科科技有限公司 | Soft package electrochemical capacitor |
| KR20090118200A (en) * | 2008-05-13 | 2009-11-18 | 엠파워(주) | Method of manufacturing carbon aerogel and the carbon aerogel manufactured using the same |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN102496703A (en) * | 2011-12-31 | 2012-06-13 | 天津得瑞丰凯新材料科技有限公司 | Multiple doped carbon cathode active material and negative electrode used for lithium battery as well as preparation method thereof |
| CN109075309A (en) * | 2016-11-23 | 2018-12-21 | 皓智环球有限公司(中国香港) | Method of the preparation for the anode slurry of secondary cell |
-
2023
- 2023-03-17 CN CN202310266285.2A patent/CN116314624A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090118200A (en) * | 2008-05-13 | 2009-11-18 | 엠파워(주) | Method of manufacturing carbon aerogel and the carbon aerogel manufactured using the same |
| CN201294156Y (en) * | 2008-09-12 | 2009-08-19 | 东莞市迈科科技有限公司 | Soft package electrochemical capacitor |
| CN101376498A (en) * | 2008-10-07 | 2009-03-04 | 同济大学 | Carbon aerogel and preparation of lithium ion button shape cell with the carbon aerogel as cathode |
| CN101847513A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece |
| CN102496703A (en) * | 2011-12-31 | 2012-06-13 | 天津得瑞丰凯新材料科技有限公司 | Multiple doped carbon cathode active material and negative electrode used for lithium battery as well as preparation method thereof |
| CN109075309A (en) * | 2016-11-23 | 2018-12-21 | 皓智环球有限公司(中国香港) | Method of the preparation for the anode slurry of secondary cell |
Non-Patent Citations (1)
| Title |
|---|
| 黄舜天 等: "碳气凝胶在电化学领域中的应用研究进展", 材料导报, vol. 32, 31 May 2018 (2018-05-31), pages 10 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109638344B (en) | Organic gel polymer electrolyte, preparation method and application thereof, sodium-based dual-ion battery and preparation method thereof | |
| JP5206758B2 (en) | Negative electrode material, metal secondary battery, and negative electrode material manufacturing method | |
| CN108172833B (en) | Zinc-based dual-ion battery and preparation method thereof | |
| EP2835855B1 (en) | Lithium-air battery and preparation method therefor | |
| CN103280601B (en) | Method for manufacturing lithium-sulfur battery | |
| CN101868873A (en) | Porous network negative electrodes for non-aqueous electrolyte secondary battery | |
| CN110729439A (en) | Preparation method of coating type MOFs (metal-organic frameworks)/organic composite diaphragm | |
| CN108649240B (en) | Fuel cell | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN107706378B (en) | Preparation method and application of high-performance porous lithium-sulfur battery positive electrode material based on carbon/oxygen-rich functional groups | |
| CN104157851A (en) | Lithium sulfur battery adopting stannous sulfide as anchoring center and preparation method of positive electrode of lithium sulfur battery | |
| CN111554905B (en) | Preparation method, product and application of zinc oxide-based carbon composite nano material | |
| CN116190633B (en) | Layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application | |
| JP2022076603A (en) | Electrolytic solution for lithium-sulfur secondary battery and lithium-sulfur secondary battery | |
| CN103490071B (en) | Lithium-Polyaniline Secondary Battery and preparation method thereof | |
| US20140356737A1 (en) | Lithium-Air Battery and Preparation Method Thereof | |
| CN112242590A (en) | Preparation method of lithium-sulfur battery interlayer material and lithium-sulfur battery | |
| CN116885273A (en) | Zeolite imidazole ester skeleton-ionic liquid composite gel electrolyte and preparation method thereof | |
| JP2012253072A (en) | Lithium ion capacitor | |
| CN116314624A (en) | Preparation method of miniature flexible lithium ion battery based on carbon aerogel | |
| CN111384368A (en) | Carbon-selenium composite material, preparation method thereof and application thereof in lithium-selenium battery | |
| JP4779327B2 (en) | ELECTRODE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY USING THE ELECTRODE | |
| CN110571500B (en) | Lithium-sulfur semi-flow battery | |
| CN111063885B (en) | Aqueous calcium ion battery positive electrode material, aqueous calcium ion battery positive electrode, and aqueous calcium ion battery | |
| JP2015032545A (en) | Nonaqueous electrolyte secondary battery |
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 |