CN104882588A - Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof - Google Patents
Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104882588A CN104882588A CN201510308966.6A CN201510308966A CN104882588A CN 104882588 A CN104882588 A CN 104882588A CN 201510308966 A CN201510308966 A CN 201510308966A CN 104882588 A CN104882588 A CN 104882588A
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- carbon
- composite membrane
- carbon nanotube
- nanotube composite
- 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
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 90
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 68
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000012528 membrane Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 72
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- -1 carbon nano-tube compound Chemical class 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 14
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon fiber/carbon nanotube composite membrane as well as a preparation method and application thereof. The preparation method comprises the following steps of adding polyacrylonitrile into N,N-dimethylformamide as organic solvent, heating the mixed solution to be 30 to 60DEG C, stirring the mixed solution until the polyacrylonitrile is completely dissolved, and configuring to obtain a polyacrylonitrile solution with the mass fraction of 7 to 12 percent; then adding 0 to 20 percent of carbon nanotube counted according to the weight of the polyacrylonitrile into the polyacrylonitrile solution for continuously stirring, and performing electrostatic spinning on the solution to obtain a polyacrylonitrile/carbon nanotube composite membrane; performing preoxidation on the polyacrylonitrile/carbon nanotube composite membrane at the temperature of 200 to 300DEG C for 0.5 to 8 hours, and carbonizing the preoxidized polyacrylonitrile/carbon nanotube composite membrane at the temperature of 600 to 1,100DEG C for 1 to 12 hours to obtain the carbon fiber/carbon nanotube composite membrane. According to the carbon fiber/carbon nanotube composite membrane disclosed by the invention, a carbon fiber/carbon nanotube is taken as a cathode material of a lithium ion battery, and the specific capacity of the lithium ion battery is 1,850 to 2,459mAh/g.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material, have and relate to a kind of carbon fiber/carbon nanotube composite membrane and preparation method thereof and the application of this composite membrane as lithium ion battery negative material.
Background technology
Energy density and the low cost of lithium ion battery Yin Qigao cause people to study interest greatly.As energy storage and conversion equipment, lithium ion battery at portable electric appts (as mobile phone, computer, camera etc.) in market in occupation of leading position, and be expected to for electric motor car, in hybrid vehicle and regenerative resource (as wind energy, solar energy etc.) large-scale energy storage device, be with a wide range of applications.However, still there is many problems and tips in lithium ion battery.On the one hand, business-like negative material graphite at present, its theoretical specific capacity is only 372mAh g
-1, the demand of market to lithium ion battery high-energy-density cannot be met.On the other hand, existing electronic equipment is not only sought progressive in performance, the breakthrough more in emphasized in design, as more frivolous more flexible bent wearable etc.And its power supply--lithium ion battery is mostly column type, prismatic and button-shaped, its intrinsic shape and heavier quality are difficult to realize this design and change.Therefore, be necessary to do further improvement to lithium ion battery especially negative material.
Carbon materials is as Graphene, and carbon nano-tube, mesoporous carbon, the conductivity of the Yin Qigao such as carbon fiber and large specific area, show good chemical property, becomes the most optimum materials substituting graphite cathode at present.But the most preparation method of these materials is complicated at present, applies limited.The present invention is by effective process and approach, carbon nano-tube is added in carbon matrix precursor, by simple electrostatic spinning, then pre-oxidation and carbonization thus obtain even carbon nanotube and be distributed in laminated film in carbon fiber network configuration, this film has good pliability, can bend arbitrarily, be directly used in lithium ion battery negative material and do not added any bonding agent or conductive additive, not only simplify the production process of electrode material, and substantially increase specific capacity and the cycle performance of lithium ion battery, simultaneously its pliable and tough bent characteristic makes the shape of lithium ion battery be undertaken by the demand that people are different designing and is not only confined to traditional button-shaped, column type or prism.
Summary of the invention
The object of the invention is to overcome existing graphite as anode material for lithium-ion battery specific capacity low, cell shapes designs limited shortcoming, by simple method of electrostatic spinning, obtain flexible self-supporting carbon fiber/carbon nanotube composite negative pole material, greatly simplify lithium ion battery electrode material preparation section, improve the specific capacity of lithium ion battery and cycle performance, thus design the lithium ion battery that shape and performance more can meet the need of market, promote the extensive use of lithium ion battery.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
A preparation method for carbon fiber/carbon nanotube composite membrane, comprises the following steps:
Steps A: the preparation of polyacrylonitrile/carbon nano-tube compound film
Polyacrylonitrile is added in organic solvent DMF, be heated to temperature 30 ~ 60 DEG C, be stirred to polyacrylonitrile and all dissolve, configure to obtain the polyacrylonitrile solution of mass fraction 7 ~ 12%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% is added in polyacrylonitrile solution, continue to stir, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube compound film;
Step B: the pre-oxidation of polyacrylonitrile/carbon nano-tube compound film and carbonization
By the polyacrylonitrile/carbon nano-tube compound film of steps A pre-oxidation 0.5 ~ 8h at temperature 200 ~ 300 DEG C, then carbonization 1 ~ 12h at temperature 600 ~ 1100 DEG C, obtains described carbon fiber/carbon nanotube composite membrane.
According to a specific embodiment of the present invention, the molecular weight of described polyacrylonitrile is 20000 ~ 150000Da.
According to a specific embodiment of the present invention, the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% being added the mixing time after polyacrylonitrile solution is 0.5 ~ 30h.
According to a specific embodiment of the present invention, the optimum configurations of described electrostatic spinning is as follows: voltage, 12 ~ 25KV; Solution fltting speed, 0.1 ~ 1mL/h; Fiber collecting distance, 10 ~ 25cm; The mode of fiber collecting is flat panel collector, cylinder is collected, roller is collected or aluminium wire is collected.
According to a specific embodiment of the present invention, described pre-oxidation carries out under the atmosphere of oxygen or air.
According to a specific embodiment of the present invention, described carbonization carries out under the atmosphere of nitrogen, argon gas, helium, neon, Krypton or xenon.
Present invention also offers a kind of preparation method by described carbon fiber/carbon nanotube composite membrane to prepare and the carbon fiber/carbon nanotube composite membrane that obtains, even carbon nanotube be embedded in carbon fiber network configuration, the diameter of carbon fiber is 0.1 ~ 10 μm.
Present invention also offers a kind of lithium ion battery negative material, be using after described carbon fiber/carbon nanotube composite membrane cutting as lithium ion battery negative material.
According to a specific embodiment of the present invention, the shape after described carbon fiber/carbon nanotube composite membrane cutting is disk, annulus, rectangle, square or cable-type.
In order to make the present invention more clear, below detailed description the present invention.
A preparation method for carbon fiber/carbon nanotube composite membrane, comprises the following steps:
Steps A: the preparation of polyacrylonitrile/carbon nano-tube compound film
Polyacrylonitrile is added in organic solvent DMF, be heated to temperature 30 ~ 60 DEG C, be stirred to polyacrylonitrile and all dissolve, configure to obtain the polyacrylonitrile solution of mass fraction 7 ~ 12%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% is added in polyacrylonitrile solution, continue to stir, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube compound film;
Step B: the pre-oxidation of polyacrylonitrile/carbon nano-tube compound film and carbonization
By the polyacrylonitrile/carbon nano-tube compound film of steps A pre-oxidation 0.5 ~ 8h at temperature 200 ~ 300 DEG C, then carbonization 1 ~ 12h at temperature 600 ~ 1100 DEG C, obtains described carbon fiber/carbon nanotube composite membrane.
Polyacrylonitrile, PAN is formed through radical polymerization by monomers acrylonitrile.Outward appearance is the opaque powder of white or yellowish, is dissolved in dimethyl formamide, dimethyl sulfoxide (DMSO), sulfolane, nitric acid ethylidene ester equal solvent.It is dissolved in solution that organic solvent formed and obtains polyacrylonitrile fibre by electrospinning, because polyacrylonitrile is heated to more than 200 DEG C and non-fusible, but painted gradually, down to carbonization, therefore the most frequently used presoma of carbon fiber prepared by polyacrylonitrile.Its weatherability and sun-resistant property good, chemical-resistant reagent, particularly inorganic acid, bleaching powder, hydrogen peroxide and general organic reagent.
The organic solvent at this place is for dissolving polyacrylonitrile, and being heated to temperature 30-60 DEG C is to allow polyacrylonitrile be dissolved completely in organic solvent, continues to stir so that carbon nano-tube is scattered in polyacrylonitrile solution more equably.
The Pre oxidation of step B controls at 200 ~ 300 DEG C, is in order to stable fibers shape, guarantees that fiber shape remains unchanged in the carbonisation of follow-up higher temperature.Carrying out carbonization at 600 ~ 1100 DEG C, is in order to polyacrylonitrile fibre is converted into carbon fiber completely.In general, in certain temperature range, carburizing temperature is higher, and the carbon fiber/carbon nanotube fragility of acquisition is larger, and pliability is poorer, but conductivity is better.Pre oxidation is regulated, the pliability of film can be affected.Simultaneously to the adjustment of carburizing temperature, its conductivity will be changed.Therefore, the present invention can meet by regulating the temperature and time of pre-oxidation and carbonization to obtain pliability and conductivity the carbon fiber/carbon nanotube composite membrane that different battery structure requires.
According to a preferred embodiment of the invention, the Pre oxidation of step B controls at 220 ~ 280 DEG C, and carburizing temperature is 600 ~ 900 DEG C.
According to a specific embodiment of the present invention, the molecular weight of described polyacrylonitrile is 20000 ~ 150000Da, and according to a preferred embodiment of the invention, the molecular weight of described polyacrylonitrile is 150000Da.
When selecting molecular weight to be the reason of the polyacrylonitrile of 20000 ~ 150000Da to be the polyacrylonitrile of this molecular weight for electrostatic spinning, the viscosity of its spinning solution and surface tension are more conducive to spin uniform diameter continuous print fiber; When molecular weight, viscosity and the surface tension of its corresponding spinning solution are lower, and discontinuous and bead structure may appear in the fiber of formation, thus affects the pliability of fiber; When molecular weight is larger, its corresponding spinning solution viscosity is excessive, is difficult to form fiber.
According to a specific embodiment of the present invention, the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% being added the mixing time after polyacrylonitrile solution is 0.5 ~ 30h.According to a preferred embodiment of the invention, the carbon nano-tube of polyacrylonitrile weighing scale 2 ~ 18% is added in polyacrylonitrile solution.According to more preferred embodiment of the present invention, just the carbon nano-tube of polyacrylonitrile weighing scale 5 ~ 15% adds in polyacrylonitrile solution.
According to a specific embodiment of the present invention, the optimum configurations of described electrostatic spinning is as follows: voltage, 12 ~ 25KV; Solution fltting speed, 0.1 ~ 1mL/h; Fiber collecting distance, 10 ~ 25cm; The mode of fiber collecting is flat panel collector, cylinder is collected, roller is collected or aluminium wire is collected.
According to a specific embodiment of the present invention, described pre-oxidation carries out under the atmosphere of oxygen or air.
According to a specific embodiment of the present invention, described carbonization carries out under the atmosphere of nitrogen, argon gas, helium, neon, Krypton or xenon.
Present invention also offers a kind of preparation method by described carbon fiber/carbon nanotube composite membrane to prepare and the carbon fiber/carbon nanotube composite membrane that obtains, even carbon nanotube be embedded in carbon fiber network configuration, the diameter of carbon fiber is 0.1 ~ 10 μm.
Present invention also offers a kind of lithium ion battery negative material, be using after described carbon fiber/carbon nanotube composite membrane cutting as lithium ion battery negative material.
According to a specific embodiment of the present invention, the shape after described carbon fiber/carbon nanotube composite membrane cutting is disk, annulus, rectangle, square or cable-type.By carrying out the cutting of different size and shape to this film, button-shaped, column type, prismatic can be designed, wire, the multiple battery such as sheet or Soft Roll structure.
When making button battery, carbon fiber/carbon nanotube composite membrane the present invention can prepared is cut to disc-shaped; When making soft-package battery, carbon fiber/carbon nanotube composite membrane the present invention can prepared is cut to rectangle or square etc.
The performance test experiment related in the present invention is as follows:
Test 1:CR2032 type button battery test system
Carbon fiber/carbon nanotube composite membrane the present invention obtained is cut into the disk or annulus that diameter is 6-20mm, be to electrode with metal lithium sheet, the carbon fiber/carbon nanotube composite membrane that the present invention obtains is negative pole, polypropylene film (Celgard2400) is barrier film, is assembled into CR2032 type button battery in the glove box being full of argon gas.
In the electrolytic solution, to circulate 50-300 time under the current density of 0.05-5A/g, test specific capacity.Battery constant current charging-discharging test voltage scope is 0.0-3.0V.
The preparation method of described electrolyte is by 1M lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio V:V=1:1).
Test 2: soft-package battery test system
Carbon fiber/carbon nanotube composite membrane the present invention obtained is cut into rectangle or square, corresponding rectangle or square-shaped metal lithium sheet are to electrode, the carbon fiber/carbon nanotube composite membrane that the present invention obtains is negative pole, polypropylene film (Celgard2400) is barrier film, and in the glove box being full of argon gas, plastic-aluminum envelope forms soft-package battery.
In the electrolytic solution, to circulate 50-300 time under the current density of 0.05-5A/g, test specific capacity.Battery constant current charging-discharging test voltage scope is 0.0-3.0V.
The preparation method of described electrolyte is by 1M lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio V:V=1:1).
The present invention compared with prior art, has following beneficial effect:
1) the present invention adds carbon nano-tube in carbon precursor, once preparation forms the combination electrode material of carbon fiber and carbon nano-tube, avoid the secondary compound of carbon fiber and carbon nano-tube, simplify preparation technology, improve carbon nano-tube dispersing uniformity in the carbon fibers;
2) conditions such as the present invention can by regulating the mass fraction of carbon matrix precursor, the addition of pre-oxidation and carburizing temperature, time and carbon nano-tube obtain the different electrode material of suppleness, meet different structure designs and the purposes of lithium ion battery;
3) the present invention can regulate electrostatic spinning voltage, advances speed, collects the carbon fiber/carbon nanotube that the technological parameters such as distance and gatherer prepare different-diameter, has more practicality, is easy to large-scale industrial and produces;
4) carbon fiber/carbon nanotube of the present invention is as the negative material of lithium ion battery, and the specific capacity of lithium ion battery is 1850 ~ 2459mAh/g.
Accompanying drawing explanation
Fig. 1 is the SEM figure of carbon fiber/carbon nanotube composite membrane prepared by the embodiment of the present invention 1.
Fig. 2 is the charging and discharging curve of carbon fiber/carbon nanotube composite membrane as the CR2032 type button cell of CR2032 type button cell cathode material of the embodiment of the present invention 1 preparation.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1
The polyacrylonitrile of molecular weight 150000Da is added in organic solvent DMF, is heated to temperature 60 C and under magnetic agitation, is stirred to polyacrylonitrile all dissolves the polyacrylonitrile solution obtaining mass fraction 10%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 5% is added in polyacrylonitrile solution, continue stirring 24 hours, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube, the optimum configurations of electrostatic spinning is as follows: applying voltage is 15kV, solution fltting speed is 0.5mL/h, fiber collecting distance is 15cm, adopts flat panel collector; By the polyacrylonitrile/carbon nano-tube compound film pre-oxidation 3h at temperature 280 DEG C in air atmosphere obtained, then carbonization 3h at temperature 900 DEG C in a nitrogen atmosphere, obtain the carbon fiber/carbon nanotube composite membrane that diameter is 0.1-0.5 μm, its pattern as shown in Figure 1.
Carbon fiber/carbon nanotube composite membrane the present invention obtained is cut into the disk that diameter is 6 ~ 20mm, is assembled into CR2032 type button cell in the glove box being full of argon gas.
Be to electrode with metal lithium sheet, the carbon fiber/carbon nanotube composite membrane that the present invention obtains is negative pole, and polypropylene film (Celgard2400) is barrier film, in the electrolytic solution, to circulate 50 times under the current density of 0.05A/g, and test specific capacity.
The battery that the present embodiment obtains first discharge capacity reaches 2459mAh/g, and after 50 circulations, specific capacity is 1097.7mAh/g, and charging and discharging curve as shown in Figure 2.
Embodiment 2
Molecular weight 150000Da polyacrylonitrile is added in organic solvent DMF, is heated to temperature 30 DEG C and under magnetic agitation, is stirred to polyacrylonitrile all dissolves the polyacrylonitrile solution obtaining mass fraction 7%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 20% is added in polyacrylonitrile solution, continue stirring 30 hours, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube, the optimum configurations of electrostatic spinning is as follows: applying voltage is 12kV, solution fltting speed is 0.1mL/h, fiber collecting distance is 10cm, adopts cylinder to collect; By polyacrylonitrile/carbon nano-tube compound film of obtaining under oxygen atmosphere at temperature 200 DEG C pre-oxidation 0.5h, then carbonization 1h at temperature 600 DEG C in a nitrogen atmosphere, obtain the carbon fiber/carbon nanotube composite membrane that diameter is 0.3-2 μm.
Carbon fiber/carbon nanotube composite membrane the present invention obtained is cut into the disk that diameter is 6 ~ 20mm, is assembled into CR2032 type button cell in the glove box being full of argon gas.
Be to electrode with metal lithium sheet, the carbon fiber/carbon nanotube composite membrane that the present invention obtains is negative pole, and polypropylene film (Celgard2400) is barrier film, in the electrolytic solution, to circulate 300 times under the current density of 0.1A/g, and test specific capacity.
The battery that the present embodiment obtains first discharge capacity reaches 1850mAh/g, and after 50 circulations, specific capacity is 640mAh/g.
Embodiment 3
Molecular weight 150000Da polyacrylonitrile is added in organic solvent DMF, is heated to temperature 40 DEG C and under magnetic agitation, is stirred to polyacrylonitrile all dissolves the polyacrylonitrile solution obtaining mass fraction 8.5%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 10% is added in polyacrylonitrile solution, continue stirring 10 hours, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube, the optimum configurations of electrostatic spinning is as follows: applying voltage is 20kV, solution fltting speed is 0.8mL/h, fiber collecting distance is 20cm, adopts roller to collect; By the polyacrylonitrile/carbon nano-tube compound film pre-oxidation 6h at temperature 220 DEG C in air atmosphere obtained, then carbonization 12h at temperature 800 DEG C in a nitrogen atmosphere, obtains the carbon fiber/carbon nanotube composite membrane that diameter is 1-5 μm.
The carbon fiber/carbon nanotube composite membrane obtained by the present embodiment is cut into the rectangular pieces of 1*3cm, in the glove box being full of argon gas, be assembled into soft-package battery.
Be to electrode with metal lithium sheet, the carbon fiber/carbon nanotube composite membrane that the present invention obtains is negative pole, and polypropylene film (Celgard2400) is barrier film, in the electrolytic solution, to circulate 100 times under the current density of 0.5A/g, and test specific capacity.
The battery that the present embodiment obtains first discharge capacity reaches 1930mAh/g, and after 50 circulations, specific capacity is 720mAh/g.
The soft-package battery that the present embodiment obtains is bent, and can lightening LED lamp.
Comparative example:
Polyacrylonitrile is added in organic solvent DMF, is heated to temperature 50 C and under magnetic agitation, is stirred to polyacrylonitrile all dissolves the polyacrylonitrile solution obtaining mass fraction 12%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 0% is added in polyacrylonitrile solution, continue stirring 0.5 hour, then this solution electrostatic spinning is obtained described polyacrylonitrile, the optimum configurations of electrostatic spinning is as follows: applying voltage is 25kV, solution fltting speed is 1.0mL/h, fiber collecting distance is 25cm, adopts aluminium wire to collect; By the polyacrylonitrile film pre-oxidation 8h at temperature 250 DEG C in air atmosphere obtained, then carbonization 6h at temperature 1100 DEG C under an argon atmosphere, obtains the carbon fiber film that diameter is 3-10 μm.
The carbon fiber film obtained by the present embodiment is cut into the rectangular bars of 1*5cm, by into a line for several this rectangular bars volume, be to electrode with metal lithium sheet, the carbon fiber film that the present invention obtains is negative pole, polypropylene film (Celgard2400) is barrier film, in the electrolytic solution, is rolled into the battery of cable shape, to circulate 500 times under the current density of 5A/g, test specific capacity.
The battery that the present embodiment obtains first discharge capacity reaches 300mAh/g, and after 50 circulations, specific capacity is 200mAh/g.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably execution mode, embodiments of the present invention are not restricted to the described embodiments, should be appreciated that, those skilled in the art can design a lot of other amendment and execution mode, these amendments and execution mode will drop within spirit disclosed in the present application and spirit.
Claims (9)
1. a preparation method for carbon fiber/carbon nanotube composite membrane, is characterized in that this preparation method comprises the following steps:
Steps A: the preparation of polyacrylonitrile/carbon nano-tube compound film
Polyacrylonitrile is added in organic solvent DMF, be heated to temperature 30 ~ 60 DEG C, be stirred to polyacrylonitrile and all dissolve, configure to obtain the polyacrylonitrile solution of mass fraction 7 ~ 12%; Subsequently the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% is added in polyacrylonitrile solution, continue to stir, then this solution electrostatic spinning is obtained described polyacrylonitrile/carbon nano-tube compound film;
Step B: the pre-oxidation of polyacrylonitrile/carbon nano-tube compound film and carbonization are by the polyacrylonitrile/carbon nano-tube compound film of steps A pre-oxidation 0.5 ~ 8h at temperature 200 ~ 300 DEG C, then carbonization 1 ~ 12h at temperature 600 ~ 1100 DEG C, obtains described carbon fiber/carbon nanotube composite membrane.
2. the preparation method of carbon fiber/carbon nanotube composite membrane according to claim 1, is characterized in that the molecular weight of described polyacrylonitrile is 20000 ~ 150000Da.
3. the preparation method of carbon fiber/carbon nanotube composite membrane according to claim 1, is characterized in that the carbon nano-tube of polyacrylonitrile weighing scale 0 ~ 20% being added the mixing time after polyacrylonitrile solution is 0.5 ~ 30h.
4. the preparation method of carbon fiber/carbon nanotube composite membrane according to claim 1, is characterized in that the optimum configurations of described electrostatic spinning is as follows: voltage, 12 ~ 25KV; Solution fltting speed, 0.1 ~ 1mL/h; Fiber collecting distance, 10 ~ 25cm; The mode of fiber collecting is flat panel collector, cylinder is collected, roller is collected or aluminium wire is collected.
5. the preparation method of carbon fiber/carbon nanotube composite membrane according to claim 1, is characterized in that described pre-oxidation carries out under the atmosphere of oxygen or air.
6. the preparation method of carbon fiber/carbon nanotube composite membrane according to claim 1, is characterized in that described carbonization carries out under the atmosphere of nitrogen, argon gas, helium, neon, Krypton or xenon.
7. the carbon fiber/carbon nanotube composite membrane obtained by preparation method's preparation of the carbon fiber/carbon nanotube composite membrane described in any one of claim 1-6, what it is characterized in that even carbon nanotube is embedded in carbon fiber network configuration, and the diameter of carbon fiber is 0.1 ~ 10 μm.
8. a lithium ion battery negative material, it is characterized in that using after carbon fiber/carbon nanotube composite membrane according to claim 7 cutting as lithium ion battery negative material.
9. lithium ion battery negative material according to claim 8, is characterized in that the shape after described carbon fiber/carbon nanotube composite membrane cutting is disk, annulus, rectangle, square or cable-type.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510308966.6A CN104882588A (en) | 2015-06-08 | 2015-06-08 | Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510308966.6A CN104882588A (en) | 2015-06-08 | 2015-06-08 | Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104882588A true CN104882588A (en) | 2015-09-02 |
Family
ID=53949990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510308966.6A Pending CN104882588A (en) | 2015-06-08 | 2015-06-08 | Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104882588A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268636A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | Carbon nano-fiber adsorbing material of aminated carbon nano tube doping and preparation method thereof |
| CN106592110A (en) * | 2016-12-29 | 2017-04-26 | 嘉兴德扬生物科技有限公司 | Preparation and application of high-strength carbon nano tube-polyacrylonitrile hybrid nanofiber membrane |
| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN107099758A (en) * | 2017-03-18 | 2017-08-29 | 华南理工大学 | A kind of continuous reinforced aluminum matrix composites of CNT/carbon fiber and preparation method thereof |
| CN107732104A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for the positive pole feature interlayer being applied in lithium-sulfur cell |
| CN110197899A (en) * | 2019-06-20 | 2019-09-03 | 荆门市亿美工业设计有限公司 | A kind of preparation method of lithium foil |
| CN111900390A (en) * | 2020-05-29 | 2020-11-06 | 湘潭大学 | A kind of metal tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application |
| CN113015617A (en) * | 2018-08-17 | 2021-06-22 | Cence公司 | Novel carbon nanofibers and method of making |
| CN113224292A (en) * | 2021-02-02 | 2021-08-06 | 江西理工大学 | High-performance lithium ion battery polyacrylonitrile carbon fiber negative electrode material and preparation method thereof |
| CN114212773A (en) * | 2021-12-17 | 2022-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nanotube film |
| WO2022061531A1 (en) * | 2020-09-22 | 2022-03-31 | 宁德新能源科技有限公司 | Negative electrode composite material, negative electrode, electro-chemical device, and electronic device |
| CN115377410A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Self-supporting lithium sulfide/conductive carbon material/carbon nanofiber composite film and its preparation method and application |
| CN115896554A (en) * | 2022-10-14 | 2023-04-04 | 山东创新金属科技有限公司 | Aluminum alloy material for high-strength corrosion-resistant automobile structural member and preparation method thereof |
| CN118725492A (en) * | 2024-07-10 | 2024-10-01 | 广州港申新材料有限公司 | A nano-modified stretch-resistant light-proof film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1886537A (en) * | 2003-10-16 | 2006-12-27 | 阿克伦大学 | Carbon nanotubes on carbon nanofiber substrate |
| CN1912200A (en) * | 2006-08-15 | 2007-02-14 | 浙江大学 | Nano-fibre of carbon nanotube and its method of preparation and oxidation reduction fix |
| CN101817517A (en) * | 2009-02-27 | 2010-09-01 | 财团法人工业技术研究院 | Method for forming carbon nanofibers |
| CN101969123A (en) * | 2010-09-17 | 2011-02-09 | 北京化工大学 | C/C coaxial nano-fiber composite membrane cathode material for lithium battery and preparation method thereof |
| CN102074683A (en) * | 2010-12-10 | 2011-05-25 | 江南大学 | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof |
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | A preparation method of activated carbon fiber membrane with hierarchical pore structure |
| CN102634873A (en) * | 2012-04-18 | 2012-08-15 | 江南大学 | Nano titanium dioxide coated carbon nanotube reinforced carbon nanofiber and preparation method thereof |
| CN103485074A (en) * | 2013-08-09 | 2014-01-01 | 天津工业大学 | Device and method of preparing electrostatic spinning polymer/inorganic particle nano-composite film |
| CN104674383A (en) * | 2015-02-12 | 2015-06-03 | 中国科学院城市环境研究所 | Carbon nano fiber aerogel electrostatic spinning construction method |
-
2015
- 2015-06-08 CN CN201510308966.6A patent/CN104882588A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1886537A (en) * | 2003-10-16 | 2006-12-27 | 阿克伦大学 | Carbon nanotubes on carbon nanofiber substrate |
| CN1912200A (en) * | 2006-08-15 | 2007-02-14 | 浙江大学 | Nano-fibre of carbon nanotube and its method of preparation and oxidation reduction fix |
| CN101817517A (en) * | 2009-02-27 | 2010-09-01 | 财团法人工业技术研究院 | Method for forming carbon nanofibers |
| CN101969123A (en) * | 2010-09-17 | 2011-02-09 | 北京化工大学 | C/C coaxial nano-fiber composite membrane cathode material for lithium battery and preparation method thereof |
| CN102074683A (en) * | 2010-12-10 | 2011-05-25 | 江南大学 | Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof |
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| CN102505403A (en) * | 2011-09-29 | 2012-06-20 | 大连理工大学 | A preparation method of activated carbon fiber membrane with hierarchical pore structure |
| CN102634873A (en) * | 2012-04-18 | 2012-08-15 | 江南大学 | Nano titanium dioxide coated carbon nanotube reinforced carbon nanofiber and preparation method thereof |
| CN103485074A (en) * | 2013-08-09 | 2014-01-01 | 天津工业大学 | Device and method of preparing electrostatic spinning polymer/inorganic particle nano-composite film |
| CN104674383A (en) * | 2015-02-12 | 2015-06-03 | 中国科学院城市环境研究所 | Carbon nano fiber aerogel electrostatic spinning construction method |
Non-Patent Citations (1)
| Title |
|---|
| SABINA PRILUTSKY ET AL.: "The effect of embedded carbon nanotubes on the morphological evolution during the carbonization of poly(acrylonitrile) nanofibers", 《NANOTECHNOLOGY》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268636B (en) * | 2016-08-12 | 2019-01-11 | 东华大学 | The carbon nano-fiber adsorbent material and preparation method thereof of aminated carbon nano tube doping |
| CN106268636A (en) * | 2016-08-12 | 2017-01-04 | 东华大学 | Carbon nano-fiber adsorbing material of aminated carbon nano tube doping and preparation method thereof |
| CN106784615B (en) * | 2016-11-18 | 2020-08-04 | 深圳大学 | Flexible lithium ion battery cathode, preparation method thereof and flexible lithium ion battery |
| CN106784615A (en) * | 2016-11-18 | 2017-05-31 | 深圳大学 | A kind of flexible lithium ion battery negative pole and preparation method thereof and flexible lithium ion battery |
| CN106592110A (en) * | 2016-12-29 | 2017-04-26 | 嘉兴德扬生物科技有限公司 | Preparation and application of high-strength carbon nano tube-polyacrylonitrile hybrid nanofiber membrane |
| CN107099758A (en) * | 2017-03-18 | 2017-08-29 | 华南理工大学 | A kind of continuous reinforced aluminum matrix composites of CNT/carbon fiber and preparation method thereof |
| CN107732104A (en) * | 2017-09-27 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of preparation method for the positive pole feature interlayer being applied in lithium-sulfur cell |
| CN113015617A (en) * | 2018-08-17 | 2021-06-22 | Cence公司 | Novel carbon nanofibers and method of making |
| CN113015617B (en) * | 2018-08-17 | 2023-07-04 | Cence公司 | Carbon nanofiber and method for producing the same |
| CN110197899A (en) * | 2019-06-20 | 2019-09-03 | 荆门市亿美工业设计有限公司 | A kind of preparation method of lithium foil |
| CN110197899B (en) * | 2019-06-20 | 2021-11-09 | 荆门市亿美工业设计有限公司 | Preparation method of lithium foil |
| CN111900390A (en) * | 2020-05-29 | 2020-11-06 | 湘潭大学 | A kind of metal tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application |
| CN111900390B (en) * | 2020-05-29 | 2022-04-01 | 湘潭大学 | Metallic tin and carbon nanotube co-doped lithium-sulfur battery interlayer material and preparation method and application thereof |
| WO2022061531A1 (en) * | 2020-09-22 | 2022-03-31 | 宁德新能源科技有限公司 | Negative electrode composite material, negative electrode, electro-chemical device, and electronic device |
| CN113224292A (en) * | 2021-02-02 | 2021-08-06 | 江西理工大学 | High-performance lithium ion battery polyacrylonitrile carbon fiber negative electrode material and preparation method thereof |
| CN115377410A (en) * | 2021-05-21 | 2022-11-22 | 中国石油化工股份有限公司 | Self-supporting lithium sulfide/conductive carbon material/carbon nanofiber composite film and its preparation method and application |
| CN114212773A (en) * | 2021-12-17 | 2022-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nanotube film |
| CN115896554A (en) * | 2022-10-14 | 2023-04-04 | 山东创新金属科技有限公司 | Aluminum alloy material for high-strength corrosion-resistant automobile structural member and preparation method thereof |
| CN115896554B (en) * | 2022-10-14 | 2024-02-20 | 山东创新金属科技有限公司 | High-strength corrosion-resistant aluminum alloy material for automobile structural member and preparation method thereof |
| CN118725492A (en) * | 2024-07-10 | 2024-10-01 | 广州港申新材料有限公司 | A nano-modified stretch-resistant light-proof film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104882588A (en) | Carbon fiber/carbon nanotube composite membrane as well as preparation method and application thereof | |
| Chen et al. | Electroactive polymeric nanofibrous composite to drive in situ construction of lithiophilic SEI for stable lithium metal anodes | |
| CN107611340B (en) | Flexible all-solid-state battery and preparation method thereof | |
| CN109119603B (en) | Composite negative electrode material, preparation method thereof, lithium ion secondary battery negative electrode piece and lithium ion secondary battery | |
| CN107611434B (en) | Preparation method and application of a flexible self-supporting porous carbon nanofiber electrode | |
| CN102315424B (en) | Composite anode material for lithium sulfur battery, preparation method and application thereof | |
| CN104681787B (en) | Lithium ion battery self-supporting silicon based anode material of plural layers and preparation method thereof | |
| Yang et al. | Synthesis of uniform polycrystalline tin dioxide nanofibers and electrochemical application in lithium-ion batteries | |
| Feng et al. | In situ XRD observation of CuO anode phase conversion in lithium-ion batteries | |
| CN105514369A (en) | A kind of hollow SnO2/Co3O4 hybrid nanotube and its preparation method and application | |
| CN102127828A (en) | Porous nano carbon fiber material, lithium battery cathode material and cathode plate | |
| CN105470484B (en) | The preparation method of graphene/tin ash composite nano-fiber membrane and application | |
| CN104269526A (en) | Preparation of polyacrylonitrile/lignin carbon nanofiber electrode for sodium ion battery | |
| CN112467200B (en) | Lithium fluoride/lithium lanthanum titanate nanofiber solid electrolyte interface material and preparation method and application thereof | |
| CN115275189A (en) | Nitrogen-doped rice hull-based hard carbon negative electrode material and preparation method and application thereof | |
| CN111900326A (en) | Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery | |
| CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof | |
| CN108258217A (en) | A kind of preparation method and application of the nanofiber rich lithium manganese base solid solution positive electrode of Sr doping | |
| CN108649210A (en) | A kind of preparation method of low self-discharge lithium cell cathode material | |
| CN113328101A (en) | Zinc/graphene three-dimensional composite structure cathode for zinc battery and preparation method thereof | |
| CN111945252B (en) | Method for preparing hollow antimony-based binary alloy composite nanofiber material based on electrostatic spinning and potassium storage application thereof | |
| WO2016110111A1 (en) | Manufacturing method of carbon fiber fabric used as cathode sheet of lithium ion battery | |
| CN101414679A (en) | Composite material and preparation method thereof, and cathode and lithium battery | |
| CN107881600B (en) | Preparation method and application of nano carbon fiber for lithium ion battery cathode | |
| Yang et al. | Natural wood-derived free-standing films as efficient and stable separators for high-performance lithium ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150902 |
|
| RJ01 | Rejection of invention patent application after publication |