CN110197898B - Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material - Google Patents
Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material Download PDFInfo
- Publication number
- CN110197898B CN110197898B CN201910528200.7A CN201910528200A CN110197898B CN 110197898 B CN110197898 B CN 110197898B CN 201910528200 A CN201910528200 A CN 201910528200A CN 110197898 B CN110197898 B CN 110197898B
- Authority
- CN
- China
- Prior art keywords
- sulfur
- carbon
- fiber network
- preparation
- conductive fiber
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 96
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 73
- 239000011593 sulfur Substances 0.000 claims abstract description 73
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000009792 diffusion process Methods 0.000 claims abstract description 11
- 239000000835 fiber Substances 0.000 claims description 70
- 239000013543 active substance Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 230000010355 oscillation Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 150000003464 sulfur compounds Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910007552 Li2Sn Inorganic materials 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 25
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000010358 mechanical oscillation Effects 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000010356 wave oscillation Effects 0.000 abstract description 3
- 238000000137 annealing Methods 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 239000004744 fabric Substances 0.000 description 19
- 238000011068 loading method Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- 241000208202 Linaceae Species 0.000 description 7
- 235000004431 Linum usitatissimum Nutrition 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- ISJVISYHMCSEPL-UHFFFAOYSA-N [S].S=C=S Chemical compound [S].S=C=S ISJVISYHMCSEPL-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 1
- IXFKTFOZUXKRDX-UHFFFAOYSA-N [Cu]=S.[Li] Chemical compound [Cu]=S.[Li] IXFKTFOZUXKRDX-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007493 shaping process Methods 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
- 238000001308 synthesis method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
A preparation method of a carbon-based flexible lithium-sulfur battery anode belongs to the technical field of preparation of lithium-sulfur battery materials for electrochemical energy storage. The method comprises the steps of firstly, utilizing carbon fibers to perform annealing treatment in an oxidizing atmosphere to prepare a three-dimensional conductive carbon network, taking the three-dimensional conductive carbon fiber network as a current collector, then immersing the three-dimensional conductive carbon fiber network into carbon disulfide of sulfur, enabling a sulfur solution to infiltrate a carbon fiber hole structure and evaporate to dryness through ultrasonic wave or mechanical oscillation under vacuum, and further utilizing high-temperature gas phase diffusion to diffuse the sulfur into finer gaps of the carbon fibers to form the carbon-based flexible lithium-sulfur battery anode with the sulfur uniformly distributed in the three-dimensional conductive carbon fiber network. The self-supporting electrode assembled flexible battery can maintain high and stable charge and discharge capacity under different folding angles. The preparation method of the self-supporting flexible electrode is simple to operate, is easy for large-scale production, can be widely applied to energy storage and flexible wearable equipment, and has good practical value.
Description
Technical Field
The invention belongs to the technical field of preparation of lithium-sulfur battery materials, and particularly relates to a preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material.
Background
Along with the improvement of people's material culture demand and the rapid development of science and technology, convenient light and handy portable wearable electronic product has obtained very big liking of people, including flexible folding display, electronic paper, flexible battery etc.. Therefore, the portable wearable flexible and portable energy storage device has huge market demands and space, and has great development space as a lithium ion battery with high energy density, strong safety and convenient carrying. At present, lithium cobaltate, lithium manganate,the energy density of the traditional lithium ion batteries such as lithium iron phosphate and ternary NCM/NCA is difficult to meet the use requirement of electronic equipment on the energy density, so that the development of a novel secondary battery with higher energy density is imperative. Furthermore, the geometry of current lithium ion batteries is relatively simple, typically of a fixed shape and size, which limits the development of electronic products for portable wearable applications. Especially, many small wearable smart devices and various micro-biological implantation devices require functional devices to be used under certain deformation conditions, and conventional hard lithium ion battery electrodes generally cannot meet the conditions. Therefore, in the fields of wearable devices, flexible electronics, micro biosensors and the like, development of a flexible high-energy-density energy storage device matched with the wearable device is urgently needed. Flexible carbon-based lithium-sulfur battery having approximately 1675mAh g-1Theoretical specific capacity of 2600Wh kg-1The energy-saving folding machine has the advantages of being environment-friendly, low in cost, capable of curling, folding, stretching, extruding and the like within a certain range, and is a primary scheme for solving the contradiction.
To date, research on lithium sulfur batteries at home and abroad has mainly focused on solving the following problems: (1) the electronic conductivity of sulfur and its discharge product, lithium sulfide, is low; (2) elemental sulfur (S) during charging and discharging8Density of 2.03g cm-3) With lithium sulphide (Li)2S, density 1.66g cm-3) When the two components are mutually converted, due to the difference of the structures and the densities of the two components, the volume change of about 80 percent can be generated, the electrode pulverization is easily caused by the volume expansion effect, the volume change is obvious, and the electrode is easily pulverized and falls off; (3) lithium polysulfide, an intermediate product of discharge, is easily dissolved in electrolyte, and causes a shuttle effect, thereby causing a series of performance attenuation and safety problems.
Disclosure of Invention
The invention aims to solve the problems that the traditional lithium-sulfur battery cannot be folded and bent, the conductivity of a sulfur active substance is poor, the volume of a sulfur electrode is rapidly expanded and deformed after lithium is embedded, and a lithium polysulfide intermediate product generated in the discharging process is easily dissolved in electrolyte, and provides a preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material.
According to the invention, a three-dimensional carbon-based conductive fiber network with certain strength is selected as a carrier and a conductive network of the flexible lithium-sulfur battery positive electrode material, and a sulfur active substance is uniformly dispersed in a porous structure of the conductive fiber network by a dissolving recrystallization and high-temperature diffusion method, so that the problem that the conventional lithium-sulfur battery positive electrode material cannot be bent and folded is solved. The conductive fiber network can provide a more efficient electron transport channel and slow down the volume expansion of sulfur in the charging and discharging processes, and the porous cabin effect can also increase the loading capacity of sulfur active substances and slow down the dissolution and diffusion speed of polysulfide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material comprises the following specific steps:
the method comprises the following steps: immersing a three-dimensional carbon-based conductive fiber network serving as a current collector into a solution containing a sulfur active substance; or the three-dimensional carbon-based conductive fiber network is taken as a current collector and is immersed into the solvent, and then the three-dimensional carbon-based conductive fiber network is mixed with the solution containing the sulfur active substance;
step two: under the vacuum condition, soaking a solution containing a sulfur active substance into a pore structure of the three-dimensional carbon-based conductive fiber network through oscillation, keeping the same pressure condition, and rotationally stirring and evaporating a solvent to dryness to obtain the sulfur active substance-loaded three-dimensional carbon-based conductive fiber network;
step three: further diffusing sulfur in the three-dimensional carbon-based conductive fiber network by using high-temperature diffusion in a closed high-pressure reaction kettle in vacuum or inert atmosphere, uniformly distributing the sulfur in the three-dimensional carbon-based conductive fiber network, and then cooling to room temperature to obtain a carbon-based flexible lithium-sulfur battery positive electrode material; the temperature of the high-temperature diffusion is 400-600 ℃, and the heat preservation and pressure maintaining time is 1-5 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention selects the high-conductivity carbon-based fiber material, adopts a gas phase oxidation method with low cost and high uniformity to prepare the porous three-dimensional conductive network structure material with certain strength, and the porous three-dimensional conductive network structure material is used as a carrier of the lithium-sulfur battery anode material to uniformly disperse sulfur active substances in a pore structure of the conductive network, so that the load of the material on the sulfur active substances can be increased, and the electron transport capability of the material in the charge and discharge process can be improved.
(2) The method adopts the mode of combining solvent dissolution, vacuum/negative pressure environment and ultrasonic/mechanical oscillation to uniformly disperse the sulfur active substance solution on the surface of the carbon-based material and inside the porous structure, and has better operability and uniformity compared with the traditional dissolving and mixing mode.
(3) The invention adopts the mode of melting and oscillating the dispersion sulfur for a long time and then penetrating the high-temperature part of the volatilized sulfur into the fine microporous structure to uniformly disperse the gas state in the porous structure of the carbon-based material, and the porous conductive network can slow down the dissolution and diffusion of polysulfide in the charging and discharging processes. Reduce the loss of active substances and improve the circulation stability of the material.
(4) The preparation method has the advantages of low cost of raw materials, simple process, strong operability, no pollution, controllable process, contribution to large-scale production and larger commercial application prospect.
Drawings
FIG. 1 is a graphical representation of the specific surface area BET test results of a three-dimensional porous carbon-based conductive network of the present invention;
FIG. 2 is a graph showing the results of pore size distribution tests of a three-dimensional porous carbon-based conductive network according to the present invention;
FIG. 3 is a SEM and EDS-like image of a high sulfur-loaded flexible positive electrode of the present invention;
fig. 4 is a graph showing the charge and discharge performance at 1C of the assembled flexible lithium sulfur battery of the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described more fully and in detail with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following specific examples. Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. Unless otherwise defined, the raw materials, solvents, instruments and equipment used in the present invention may be commercially available or may be prepared by existing simple methods.
The invention uses a three-dimensional conductive carbon fiber network carbon skeleton with a porous structure as an electrode current collector, sulfur active substances are dispersed in the three-dimensional porous conductive skeleton by a solvent infiltration and high-temperature diffusion method, a lithium sulfur battery electrode structure with sulfur active materials uniformly dispersed and loaded in the three-dimensional conductive carbon fiber network and on the surface is formed, and the high-sulfur-loading electrode material has high conductivity. Meanwhile, the network porous carbon structure is favorable for inhibiting the volume change of elemental sulfur in the charging and discharging process, and the cabin isolation effect of the porous structure is favorable for alleviating the problem of polysulfide dissolution in electrolyte. In addition, the specially treated three-dimensional porous conductive carbon fiber also has certain strength and flexibility, realizes high load and uniform wrapping of sulfur, and obtains good electrochemical performance.
The first embodiment is as follows: the embodiment describes a preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material, which comprises the following specific steps:
the method comprises the following steps: immersing a three-dimensional carbon-based conductive fiber network serving as a current collector into a solution containing a sulfur active substance; or the three-dimensional carbon-based conductive fiber network is taken as a current collector and is immersed into the solvent, and then the three-dimensional carbon-based conductive fiber network is mixed with the solution containing the sulfur active substance; the concentration of the solution containing the sulfur active substances is 0.05-1.5 g/mL, and the environmental temperature of the step is 5-45 ℃;
step two: under a closed vacuum condition, soaking a solution containing a sulfur active substance into a pore structure of a three-dimensional carbon-based conductive fiber network through oscillation, maintaining the same pressure condition, and rotationally stirring and evaporating a solvent to dryness to obtain a sulfur active substance-loaded three-dimensional carbon-based conductive fiber network; the oscillation is one or more of ultrasonic oscillation, mechanical high-frequency oscillation and mechanical low-frequency oscillation; the vacuum degree of the vacuum is-1 to-95 Kpa;
step three: further diffusing sulfur in the three-dimensional carbon-based conductive fiber network by using high-temperature diffusion in a closed high-pressure reaction kettle in vacuum or inert atmosphere, uniformly distributing the sulfur in the three-dimensional carbon-based conductive fiber network, and naturally cooling to room temperature to obtain a carbon-based flexible lithium-sulfur battery positive electrode material; the temperature of the high-temperature diffusion is 400-600 ℃, and the heat preservation and pressure maintaining time is 1-5 h.
The second embodiment is as follows: in a preparation method of a porous carbon-based flexible lithium sulfur battery cathode material, as shown in BET test results in fig. 1 and 2, the three-dimensional carbon-based conductive fiber network has rich pore structures, including micropores, mesopores, and macropores, and the pore structures are mainly distributed in the range of 0.5-3.5 nm micropores and mesopores.
The third concrete implementation mode: in a preparation method of a porous structure carbon-based flexible lithium sulfur battery positive electrode material, in a step one, a three-dimensional carbon-based conductive fiber network is prepared according to the following method:
carbon fibers or a material which can form high-conductivity carbon-based fibers through carbonization are used as a raw material, and the raw material is treated in an atmosphere with the oxygen volume concentration of 1-80% at the temperature of 250-610 ℃ to partially oxidize the carbon material, so that a three-dimensional carbon-based conductive fiber network with certain strength, controllable specific surface area, high conductivity and flexibility is obtained; the treatment temperature is 250-610 ℃, and the volume concentration of oxygen is 1-80%.
The three-dimensional carbon-based conductive fiber network can be carbon-based fiber with certain conductivity and strength, which is prepared by carbonizing natural cellulose fiber such as bamboo, flax, cotton yarn and the like serving as raw materials; or the carbon-based fiber with high conductivity and strength can be prepared by carbonizing synthetic fibers such as Polyacrylonitrile (PAN), azure-based carbon-based fiber (HPCF), viscose fiber and the like serving as raw materials. The carbon fiber needs to be subjected to low-temperature (250-610 ℃) hollow annealing in air, oxidized and etched to form a three-dimensional conductive carbon matrix with an active site and a micro-nano hole structure.
The fourth concrete implementation mode: detailed description of the invention A porous structure carbon-based flexible lithium sulfur batteryThe preparation method of the cell anode material is characterized in that the specific surface area of the three-dimensional carbon-based conductive fiber network is 100-1200 m2 g-1The diameter of the fiber unit is 1-100 microns.
The fifth concrete implementation mode: in the method for preparing the porous carbon-based flexible lithium-sulfur battery cathode material according to the third embodiment, the atmosphere is a gas atmosphere containing an oxidation effect. Such as air, oxygen mixed with inert gas (such as nitrogen and argon) with different partial pressures, and one or more of the above oxidizing gases with oxidizing function at 250-610 deg.C.
The sixth specific implementation mode: in a method for preparing a porous carbon-based flexible lithium-sulfur battery positive electrode material, a concentration of a solution containing a sulfur active material is 10-600 mg ml-1The sulfur loading can be regulated and controlled by adjusting the concentration of sulfur in the solution, and the mass surface density of the sulfur active substance is 0.1mg cm-2~40mg cm-2The infiltration degree of the sulfur solution can be adjusted by ultrasonic wave or mechanical oscillation treatment under negative pressure.
The seventh embodiment: in one or more embodiments of the method for preparing a porous carbon-based flexible lithium-sulfur battery positive electrode material, a solvent of a solution containing a sulfur active material is a mixture of one or more of carbon disulfide, carbon tetrachloride, toluene, cyclohexane, N-octane, dimethyl sulfoxide, acetone, xylene, ethanol, ethylene glycol, N-methylpyrrolidone, glycerol, chloroform, glacial acetic acid, propylene carbonate, ethyl methyl carbonate, propyl methyl carbonate, dimethyl carbonate, 1, 2-dimethoxyethane, acetonitrile, and critical carbon dioxide.
The specific implementation mode is eight: in the method for preparing a porous structure carbon-based flexible lithium-sulfur battery cathode material according to the first or sixth embodiment, the sulfur active material is soluble elemental sulfur and a sulfur-based compound; the elemental sulfur is one or a mixture of more of orthorhombic sulfur, amorphous sulfur, sublimed sulfur or high-purity sulfur; the sulfur-based compound is organic sulfide, Li2SnN is not less than 1, at least one of carbon-sulfur polymersAnd (4) seed preparation.
Example 1:
a preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material comprises the following specific steps:
the method comprises the following steps: taking a three-dimensional carbon-based conductive fiber network as a current collector, and immersing the current collector into a sulfur carbon disulfide solution, wherein the concentration of the sulfur carbon disulfide solution is 25g mL-1;
Step two: under the vacuum (-5 to-95 Kpa) environment, soaking solution containing elemental sulfur into a pore structure of the three-dimensional carbon-based conductive fiber network through ultrasonic oscillation (power: 500W, frequency: 40KHz), keeping the same pressure and ultrasonic conditions, and rotationally stirring and evaporating the solvent to dryness, so that the elemental sulfur can be uniformly enriched in the three-dimensional carbon-based conductive fiber network, and the sulfur-loaded three-dimensional carbon-based conductive fiber network is obtained; the set pressure condition is favorable for removing air remained in the inner pores of the three-dimensional carbon-based conductive fiber network, the air is removed more thoroughly by combining ultrasonic wave or mechanical oscillation, and meanwhile, the sulfur solution is favorably infiltrated into the inner pores of the three-dimensional carbon-based conductive fiber network, so that the sulfur is more uniformly dispersed; according to a similar compatibility principle, sulfur-containing active substances such as sulfur compounds and the like can be dissolved in one or more solvents with high solubility to sulfur such as carbon disulfide and the like, the three-dimensional porous conductive carbon fiber is soaked in the solvent, air in the porous carbon-based material is reduced by adopting methods of changing the soaking environmental pressure, shaking and the like for multiple times, and the solution containing the active substances is soaked in a hole structure of the carbon-based material as much as possible; the concentration of active substances in the solution is regulated, and the sulfur loading is regulated and controlled by means of recrystallization and the like;
step three: putting the sulfur-loaded three-dimensional carbon-based conductive fiber network obtained in the step two into a pressure-resistant container in a vacuum or inert atmosphere environment, and controlling the temperature to be 115-440 ℃ for 1-30 h; so that the sulfur penetrates into the pore structure of the carbon material in a molten state with lower viscosity. And controlling the temperature at 400-600 ℃ after the process, keeping the temperature for 1-5 hours, gasifying and uniformly diffusing part of sulfur in the pore structure of the carbon fiber, and finally quickly cooling to facilitate uniform condensation of the sulfur permeating into the pores of the carbon fiber, thereby obtaining the porous structure carbon-based flexible lithium-sulfur battery cathode material shown in figure 3.
And after assembling the obtained carbon-based flexible lithium-sulfur battery positive electrode, flexible current collectors such as flexible copper foil or foam copper and the like, a diaphragm and a lithium sheet/lithium film to obtain a bare cell, welding a tab, putting the bare cell into a shell/bag, baking, injecting liquid, standing, forming and shaping to obtain the high-energy-density flexible finished product electrochemical energy storage battery.
Example 2:
the invention discloses a preparation method of a three-dimensional carbon-based conductive fiber network, which comprises the following steps: cutting carbon cloth fiber with the thickness of 0.3mm into cloth pieces with the thickness of 10x 10cm, fixing and vertically placing the carbon cloth pieces in a corundum crucible, placing the corundum crucible in a muffle furnace, heating the corundum crucible to 400 ℃ from room temperature at the heating rate of 5 ℃/min, preserving heat for 3h, and naturally cooling to the room temperature to obtain a three-dimensional carbon-based conductive fiber network with a certain strength and a porous structure, wherein the specific surface area test of the structure is shown in figures 1 and 2.
Example 3:
the preparation method of the three-dimensional carbon-based conductive fiber network comprises the steps of preparing an artificially synthesized carbon fiber precursor by an electrostatic spinning technology, obtaining carbon-based fibers by high-temperature carbonization, and finally oxidizing the carbon-based fibers in a high-temperature gas environment to form a highly conductive carbon-based fiber network structure with a porous structure. One typical synthetic method using Polyacrylonitrile (PAN) as a raw material is as follows, which specifically comprises the following steps:
(1) first, 1g PAN was added to 10mL DMF solution and stirred at 50 ℃ for 12 h. Finally, the obtained solution is filled into a 10mL syringe, a stainless steel needle with the model number of 20 is arranged, and an electrostatic spinning instrument is arranged for spinning. The spinning accelerating voltage is set to be 13-14 kV, the distance between the needle head and the receiving body is set to be 14cm, and the injection rate is 1.2mLh-1And obtaining the PNA-based spinning precursor-fiber cloth after spinning.
(2) The PNA-based spinning precursor-fiber prepared above was coated in argon-hydrogen (Ar/H)2) Pretreating at 150 deg.C for 1 hr under mixed atmosphere, and carbonizing at 1000 deg.C for 2 hr under the same atmosphere to obtain baseFlexible three-dimensional conductive carbon fiber cloth in PAN.
(3) And (3) obtaining a PAN-based flexible porous three-dimensional carbon-based conductive fiber network by using the carbon fiber cloth obtained in the step (2) according to the method in the embodiment 2.
Example 4:
the preparation method of the three-dimensional carbon-based conductive fiber network comprises the steps of carbonizing natural cellulose fibers such as bamboo, flax, cotton yarn and the like serving as raw materials to obtain carbon-based fibers with certain conductivity and strength; the synthesis method of the typical flax fiber cloth as the raw material comprises the following steps:
(1) repeatedly and alternately cleaning flax fiber/fiber cloth with ethanol and deionized water to remove oil stain on the surface, and then washing with argon-hydrogen (Ar/H)2) Pretreating for 1h at 150 ℃ in a mixed atmosphere, and then carbonizing for 2h at 1000 ℃ in the same atmosphere condition to obtain the flax fiber-based flexible three-dimensional conductive carbon fiber cloth.
(2) And (3) obtaining the flax fiber-based flexible three-dimensional conductive carbon fiber cloth obtained in the step (2) according to the method in the embodiment 2 to obtain a flax fiber-based flexible porous three-dimensional conductive carbon fiber network.
Example 5:
the method for loading sulfur by the three-dimensional porous conductive carbon fiber network is not limited to the following illustrated examples, but also comprises the following steps of preparing the carbon-based three-dimensional conductive fiber with high loading capacity by using the method used in the following examples:
(1) 1.5g of the carbon fiber cloth with certain strength and a porous structure obtained in the example 2 is immersed in a carbon disulfide solution with the concentration of 0.25g/mL of sulfur, repeated operation is carried out under the conditions of ultrasonic oscillation (power of 1Kw) and vacuum negative pressure (-95Kpa), when obvious sulfur crystals appear at the bottom of a container or on the surface of the carbon cloth, the carbon cloth fiber is dried at 60 ℃, and the prepared carbon fiber cloth with the loading capacity of 1.26g (12.6mg cm/cm) is prepared-2) The carbon cloth of (2) carries a sulfur electrode sheet.
(2) Transferring the porous carbon fiber cloth loaded with sulfur after the step (1) to a rotatable device for hot melting for 12 hours at 155 ℃, wherein the device is used for heating and meltingThe rotation speed of the mechanical rotational vibration was 0.1min rod-1And cooling to obtain the composite material with molten sulfur uniformly dispersed in the porous mechanism of the three-dimensional porous carbon fiber.
(3) Putting the composite material obtained in the step (2) into a closed high-pressure reaction kettle, and keeping the temperature for 5 ℃ for min-1Heating to 400 deg.C, maintaining the temperature and pressure for 10 hr, and heating at 100 deg.C for min-1Rapidly cooled to room temperature to give a loading of 10.6mg cm-2The flexible positive electrode material for lithium-sulfur batteries. Bonding the high-load flexible lithium-sulfur battery positive electrode material prepared in the embodiment with an aluminum foil, welding a tab, assembling the tab, a lithium-sulfur copper foil-plated negative electrode, a diaphragm and an aluminum-plastic film to form a lithium-sulfur battery lamination bare cell, and filling electrolyte to obtain a finished product of the flexible soft package lithium-sulfur battery. And testing the prepared lithium-sulfur battery in charge-discharge, cycle performance and the like.
Example 6:
the method for loading sulfur by the three-dimensional carbon-based conductive fiber network is not limited to the substances of the following examples, which have been illustrated, but also comprises the three-dimensional carbon-based conductive fiber network with high loading capacity prepared by the method used in the following examples, and specifically comprises the following steps:
(1) the carbon fiber cloth having a certain strength and a porous structure obtained in example 2 was alternately washed with distilled water, acetone and alcohol and then vacuum-dried for use.
(2) Taking 10g of porous activated carbon material, placing the porous activated carbon material in a corundum crucible, and placing the corundum crucible in a muffle furnace for 5 ℃ min-1The temperature rising rate is increased from room temperature to 300 ℃, and the porous activated carbon material partially oxidized in the oxidizing atmosphere is obtained by naturally cooling after heat preservation for 3 hours.
(3) And mixing and uniformly stirring the oxidized 5g of porous activated carbon material with 200mL of carbon disulfide solution, then putting the mixture into a 500mL rotary evaporation bottle, adding 50mL of carbon disulfide solution dissolved with 5g of sulfur, heating the mixture to 30 ℃, and repeatedly operating under the conditions of ultrasonic oscillation (power of 1Kw) and vacuum negative pressure (-95Kpa), thus finally obtaining the porous carbon active material uniformly loaded with 5g of sulfur.
(4) And (3) fully stirring the porous activated carbon material obtained in the step (3) with a conductive agent, a binder and a solvent (insoluble sulfur) to obtain active substance slurry, and then coating the active substance slurry on the surface of the carbon fiber cloth obtained in the step (2) to obtain a certain strength and a porous structure, or coating the surface of the carbon fiber cloth obtained in the step (3) in the step (5) to obtain a flexible lithium-sulfur battery positive electrode with further increased loading capacity.
(5) The flexible lithium-sulfur battery positive electrode obtained in the step (4) is sequentially subjected to the steps (2) and (3) in the example 5 to finally obtain the flexible lithium-sulfur battery positive electrode with the loading capacity of 39mg cm-2The flexible positive electrode material for lithium-sulfur batteries.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (8)
1. A preparation method of a porous structure carbon-based flexible lithium-sulfur battery positive electrode material is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: immersing a three-dimensional carbon-based conductive fiber network serving as a current collector into a solution containing a sulfur active substance; or the three-dimensional carbon-based conductive fiber network is taken as a current collector and is immersed into the solvent, and then the three-dimensional carbon-based conductive fiber network is mixed with the solution containing the sulfur active substance;
step two: under the vacuum condition, soaking a solution containing a sulfur active substance into a pore structure of the three-dimensional carbon-based conductive fiber network through oscillation, keeping the same pressure condition, and rotationally stirring and evaporating a solvent to dryness to obtain the sulfur active substance-loaded three-dimensional carbon-based conductive fiber network;
step three: keeping the carbon-based flexible lithium-sulfur battery anode material in a sealed high-pressure reaction kettle at the temperature of 115-440 ℃ for 1-30 hours in vacuum or inert atmosphere, further diffusing sulfur in the three-dimensional carbon-based conductive fiber network by using high-temperature diffusion, uniformly distributing the sulfur in the three-dimensional carbon-based conductive fiber network, and naturally cooling to room temperature to obtain the carbon-based flexible lithium-sulfur battery anode material; the temperature of the high-temperature diffusion is 400-600 ℃, and the heat preservation and pressure maintaining time is 1-5 h.
2. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1, characterized in that: the three-dimensional carbon-based conductive fiber network comprises micropores, mesopores and macropores.
3. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1, characterized in that: in the first step, the three-dimensional carbon-based conductive fiber network is prepared according to the following method:
carbon fibers or a material which can form high-conductivity carbon-based fibers through carbonization are used as a raw material, and the raw material is treated in an atmosphere with the oxygen volume concentration of 1-80% at the temperature of 250-610 ℃ to partially oxidize the carbon material, so that a three-dimensional carbon-based conductive fiber network is obtained; the treatment temperature is 250-610 ℃, and the volume concentration of oxygen is 1-80%.
4. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1 or 3, characterized in that: the specific surface area of the three-dimensional carbon-based conductive fiber network is 100-1200 m2 g-1The diameter of the fiber unit is 1-100 microns.
5. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 3, characterized in that: the atmosphere is a gas atmosphere with an oxidation effect.
6. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1, characterized in that: the concentration of the solution containing the sulfur active substances is 10-600 mg ml-1The mass surface density of the sulfur active material is 0.1mg cm-2~40mg cm-2。
7. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1 or 6, characterized in that: the solvent of the solution containing the sulfur active substance is one or a mixture of carbon disulfide, carbon tetrachloride, toluene, cyclohexane, N-octane, dimethyl sulfoxide, acetone, xylene, ethanol, ethylene glycol, N-methyl pyrrolidone, glycerol, chloroform, glacial acetic acid, propylene carbonate, ethyl methyl carbonate, propyl methyl carbonate, dimethyl carbonate, 1, 2-dimethoxyethane and acetonitrile, and critical carbon dioxide.
8. The preparation method of the porous structure carbon-based flexible lithium-sulfur battery positive electrode material according to claim 1 or 6, characterized in that: the sulfur active material is soluble elemental sulfur and sulfur-based compounds; the elemental sulfur is one or a mixture of more of orthorhombic sulfur, amorphous sulfur, sublimed sulfur or high-purity sulfur; the sulfur-based compound is organic sulfide, Li2SnN is not less than 1, and at least one of carbon-sulfur polymers.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910528200.7A CN110197898B (en) | 2019-06-18 | 2019-06-18 | Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910528200.7A CN110197898B (en) | 2019-06-18 | 2019-06-18 | Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110197898A CN110197898A (en) | 2019-09-03 |
CN110197898B true CN110197898B (en) | 2021-03-12 |
Family
ID=67754695
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910528200.7A Active CN110197898B (en) | 2019-06-18 | 2019-06-18 | Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110197898B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110743528B (en) * | 2019-11-05 | 2022-07-29 | 珠海冠宇电池股份有限公司 | Method for preparing water decomposition catalyst by using waste battery |
CN110931795B (en) * | 2019-12-04 | 2021-03-05 | 南京工业大学 | Flexible self-supporting composite electrode and preparation method and application thereof |
CN113363454B (en) * | 2021-06-03 | 2022-03-25 | 山东海科创新研究院有限公司 | Lithium-sulfur battery positive pole piece and preparation method and application thereof |
CN114108363B (en) * | 2021-10-08 | 2023-03-21 | 华南理工大学 | Self-supporting carbon material and preparation method and application thereof |
CN114583145B (en) * | 2022-03-25 | 2023-11-03 | 江西省纳米技术研究院 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140490A (en) * | 2015-09-28 | 2015-12-09 | 中南大学 | Preparation method of lithium-sulfur battery flexible positive electrode |
WO2017116599A2 (en) * | 2015-11-30 | 2017-07-06 | University Of Maryland, College Park | Solid-state li-s batteries and methods of making same |
CN108461706A (en) * | 2018-02-26 | 2018-08-28 | 上海交通大学 | The preparation method of photonic crystal lithium-sulfur cell based on metal ordered porous structural |
CN109244455A (en) * | 2018-09-04 | 2019-01-18 | 复旦大学 | A kind of lithium-sulfur cell loads the preparation method of positive electrode with self-supporting high-sulfur |
CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
-
2019
- 2019-06-18 CN CN201910528200.7A patent/CN110197898B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105140490A (en) * | 2015-09-28 | 2015-12-09 | 中南大学 | Preparation method of lithium-sulfur battery flexible positive electrode |
WO2017116599A2 (en) * | 2015-11-30 | 2017-07-06 | University Of Maryland, College Park | Solid-state li-s batteries and methods of making same |
CN108461706A (en) * | 2018-02-26 | 2018-08-28 | 上海交通大学 | The preparation method of photonic crystal lithium-sulfur cell based on metal ordered porous structural |
CN109244455A (en) * | 2018-09-04 | 2019-01-18 | 复旦大学 | A kind of lithium-sulfur cell loads the preparation method of positive electrode with self-supporting high-sulfur |
CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
Also Published As
Publication number | Publication date |
---|---|
CN110197898A (en) | 2019-09-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110197898B (en) | Preparation method of porous structure carbon-based flexible lithium-sulfur battery positive electrode material | |
JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
CN107681142B (en) | Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof | |
Zeng et al. | Green synthesis of a Se/HPCF–rGO composite for Li–Se batteries with excellent long-term cycling performance | |
CN108615865B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
CN108574089B (en) | Preparation method of hollow tubular lithium-rich manganese-based positive electrode material | |
CN107808955B (en) | Activated carbon material with spherical structure and preparation method and application thereof | |
WO2018006557A1 (en) | Tunable and scalable synthesis of hierarchical porous nanocarbon/sulfur composite cathodes | |
CN107732104A (en) | A kind of preparation method for the positive pole feature interlayer being applied in lithium-sulfur cell | |
CN107140633A (en) | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived | |
CN106997947A (en) | A kind of self assembly polyimide porous material, preparation method and its application in lithium-sulfur cell | |
CN111785943A (en) | Preparation method and application of NPC @ C/S composite material | |
CN112615009A (en) | Flexible self-supporting lithium-tin alloy composite nanofiber lithium metal battery cathode material | |
CN105977474A (en) | Simple method for effectively improving cycling stability of carbon-sulfur composite lithium-sulfur cathode | |
CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
CN106252630A (en) | Nitrogen-rich hollow carbon sphere/sulfur composite positive electrode material for lithium-sulfur battery and preparation method thereof | |
CN106654182A (en) | Manganese dioxide sulfur-carbon positive electrode and preparation method | |
CN110350175A (en) | A kind of composite material of the graphene-supported sulphur of porous carbon@, preparation method and applications | |
CN108963226A (en) | C silicon/activity silicon/charcoal core-shell structure composite negative pole material and preparation method thereof | |
CN113097469A (en) | Preparation method of Si/SiC/C nanofiber membrane, battery cathode and lithium ion battery | |
CN112786869A (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
CN109449008B (en) | Preparation method and application of self-supporting hollow core-shell structure electrode material | |
CN115020707B (en) | Flexible lithium metal battery lithium-philic carbon nanofiber framework material and preparation method and application thereof | |
CN110336033A (en) | A kind of cell positive material and preparation method thereof, a kind of lithium-sulfur cell | |
CN111525122B (en) | NaTi2(PO4)3Negative electrode material of-porous carbon nanofiber sodium ion battery 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 | ||
CB02 | Change of applicant information | ||
CB02 | Change of applicant information |
Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai CosMX Battery Co.,Ltd. Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
|
GR01 | Patent grant | ||
GR01 | Patent grant |