CN102263221A - Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof - Google Patents
Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof Download PDFInfo
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- CN102263221A CN102263221A CN2011101701378A CN201110170137A CN102263221A CN 102263221 A CN102263221 A CN 102263221A CN 2011101701378 A CN2011101701378 A CN 2011101701378A CN 201110170137 A CN201110170137 A CN 201110170137A CN 102263221 A CN102263221 A CN 102263221A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 57
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 38
- 229920000642 polymer Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 8
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- 238000002360 preparation method Methods 0.000 claims description 19
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000007772 electrode material Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 244000010375 Talinum crassifolium Species 0.000 claims description 3
- 235000015055 Talinum crassifolium Nutrition 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 claims 1
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- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical group [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention belongs to the technical field of lithium ion batteries and in particular relates to a CNT (carbon nano tube)/polymer composite membrane as well as a preparing method and an application thereof. The composite membrane is prepared by taking an epoxy resin embedding solution, a flexibilizer and a CNT array as raw materials and then carrying out curing, compounding and slicing on the raw materials. CNTs in the composite membrane are distributed evenly, thus the upper and lower surfaces of the composite membrane have good electrical conductivity and also have good flexibility and strength; and the surfaces of the composite membrane are provided with a large number of opened tail ends of the CNTs, and the composite membrane can be applied to lithium ion batteries widely due to the highly oriented structures of the opened tail ends. The vertically-oriented CNT/polymer composite membrane is applied to buckled lithium ion batteries and polymer lithium ion batteries and also suitable for other types of lithium ion batteries.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of carbon nano-tube/polymer composite membrane and its production and application.
Background technology
The discovery of carbon nano-tube is a milestone on the World Science history.Japanese Iijima found carbon nano-tube (Carbon Nanotubes in 1991, CNTs) since [1], carbon nano-tube with its distinctive high tensile, high resiliency, from metal to semi-conductive characteristic electron, high current load amount and high heat conductor and unique accurate one dimension tracheary element structure, in following high-tech area, have many potential using values, become the focus that people pay close attention to.Carbon nano-tube is widely studied to join and prepares composite material in the polymer, but because carbon nano-tube random in polymer, the practical application performance of composite material is unsatisfactory.Along with the further investigation of carbon nano pipe array (ACNT), the macro length of nano-tube array has enough made single carbon pipe run through whole material in composite material.Utilize the order preparation of carbon nano pipe array to be uniformly dispersed, flexible carbon nano-tube/polymer composite material becomes new research focus.The method for preparing at present carbon nano-tube/polymer composite material mainly contains two kinds of in-situ polymerization and polymer infiltration methods.Can prepare the composite material with anisotropic, its superior electrical property, mechanical performance demonstrate very good application potential [2] [3].
New energy technology to human society following sustainable development bringing into play crucial effects, lithium ion battery is to develop in the 90's of last century, have the specific energy height, have extended cycle life, security performance is good, memory-less effect, advantage such as environmentally friendly, now be widely used in the portable electronics such as mobile phone, notebook computer, video camera, and be expected the storage of large-scale application in cleaning electric energy such as electric automobile and solar energy, wind energies.Lithium ion battery is since commercialization, and electrode material is the research focus of field of batteries all the time.In the embedding lithium reaction of lithium ion battery, LiC6 once was considered to the highest composition of lithium carbon compound, but the report that surpasses theoretical capacity of nano-carbon material since 1994, allow people begin the exploration of lithium ion battery negative material of new generation, wherein the research about CNT (carbon nano-tube) has obtained impressive progress.Ideally, carbon nano-tube is seamless, the hollow tube that is rolled into by graphite linings.Carbon nano-tube has high surface area and excellent mechanical performance and electric property, has been the focus of material science research field since coming out always.The charge/discharge capacity of discovering CNT (carbon nano-tube) can surpass more than a times of graphite lithium intercalation compound theoretical capacity.But the random accumulation of carbon pipe is unfavorable for the embedding lithium and takes off embedding that how effectively bringing into play the effect of carbon pipe in lithium ion battery becomes a direction [4] [5] that is subjected to extensive concern.
At how effectively bringing into play the effect of carbon pipe in lithium ion battery, the present invention is directed to the problem that existing lithium-ion battery system exists, use vertical orientated carbon pipe/composite membrane of polymer electrode material.Carbon is guaranteed the order of having held height in the kind electrode material, thereby has improved the conductivity of electrode material, and all carbon Guan Jun to remain on the two ends of film opening-like, be beneficial to improve storage lithium performance.Because polymer is fixing, the electrode that the carbon tube material is made has the advantage that the life-span is long, fail safe good, specific capacity is high, high rate performance is superior; By with composition and the process optimization of this compound film electrode in lithium ion battery applications, prepare the new type lithium ion battery of high-energy-density, high security.
Summary of the invention
The object of the present invention is to provide a kind of excellent conductive capability that has, aligned carbon nanotube/composite membrane of polymer of good flexibility and intensity and its production and application is arranged again.
The method for preparing aligned carbon nanotube/composite membrane of polymer provided by the invention.Mainly be to classify raw material as,, make resin monomer immerse array inside, then by the formation composite material that is heating and curing by the method for infiltration with the mixed solution and the carbon nano-pipe array of epoxy monomer and flexibilizer.Obtain the carbon nano-tube/polymer composite membrane with the slicing machine section at last.The innovation part of this method is, has realized the making of vertical orientated carbon nano-tube film, and the film upper and lower surface is connected by single-root carbon nano-tube, thereby brings into play the electric property of carbon nano-tube better.
The concrete steps of the inventive method are as follows:
Carbon nano pipe array is immersed the mixed solution of epoxy monomer and flexibilizer, permeate embedding; 55--65 in baking oven again
oC solidified 12--40 hour, obtained embedded block; Be cut into the different-thickness compound foil with slicing machine, obtain the carbon nano-tube/polymer composite membrane, the thickness range of composite membrane is 50 nanometers to 50 micron.
The inventive method is completely fixed in carbon nano pipe array in the epoxy resin, carbon nano-tube is equally distributed fully in the film that obtains after the section, and all perpendicular to the surface of film, therefore have very outstanding conductivity by a large amount of single-root carbon nano-tube UNICOMs between the film upper and lower surface, film surface has a large amount of carbon nano-tube open end.
Among the present invention, carbon nano pipe array can be prepared as follows:
The catalyst structure that the synthesizing carbon nanotubes array is used is Si/SiO
2/ Al
2O
3/ Fe, wherein, SiO
2Thickness is 300-1000 μ m, Al
2O
3Thickness is 10-30 nm, and Fe thickness is 0.5-1.5 nm, Al
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they deposit the film preparation acquisition of one deck nano thickness respectively on silicon chip by the electron beam evaporation deposition instrument; Adopt chemical vapour deposition technique, do carbon source, as carrier gas, synthetic height-oriented carbon nano pipe array on the oxide layer Si substrate is being arranged with argon gas and hydrogen with ethene; The therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, growth 5-100 min in tube furnace.
The carbon nano-tube/polymer composite membrane that method for preparing obtains can be used as electrode material, the lithium ion battery of packing into, preparation high-performance secondary lithium battery.Also this composite membrane gas sensor be can be prepared as senser, high sensitivity, high stability, the Sensitive Apparatus of short recovery time obtained.
One, buckle type lithium-ion battery installation steps
(1) earlier the battery stainless steel case is cleaned with distilled water, then in ultrasonic cleaner, use distilled water ultrasonic 15--25 minute, use the ultrasonic 15--25 of absolute ethyl alcohol minute again, 75--85 ℃ of oven dry in baking oven at last.
(2) be negative plate with the thick aligned carbon nanotube/composite membrane of polymer of 1～50um, in the convection oven dry 75--85 ℃ dry 4--8 hour.
(3) under the inert gas shielding environment, according to stainless steel casing, the carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, the lithium sheet, collector, the order of stainless steel cover is installed.The middle electrolyte that drips makes electrolyte fully soak into electrode and diaphragm material.
(4) mounted lithium ion battery being positioned over the ventilation lucifugal place changed into more than 20 hours.
Two, based on the making of aligned carbon nanotube/composite membrane of polymer as the polymer Li-ion battery of electrode material, concrete steps are as follows:
(1) aligned carbon nanotube/composite membrane of polymer of preparation battery product design size.
(2) cutting suitable dimension barrier film.
(3) the preparation battery is put well according to the order of positive pole/barrier film/negative pole/barrier film/positive pole or the order of negative pole/barrier film/positive pole/barrier film, makes battery through coiling/lamination.
(4) be assembled into battery, and four edges seal after injecting electrolyte or sol-electrolyte.
(5) change into and place: charging changes at a slow speed, and after placing several weeks, filters out qualified products.
Description of drawings
Fig. 1, a are the pictorial diagram of carbon nano pipe array after with resin embedding, figure b-f for the carbon nano-tube/polymer composite membrane by multi-form aspect graph after crooked or folding.
Fig. 2, battery operated schematic diagram.
Fig. 3, buckle type lithium-ion battery structure figure.
Fig. 4, polymer lithium electricity manufacturing process.
Embodiment
The detailed process of preparation is as follows:
The first, aligned carbon nanotube array synthetic.
Orthotropic carbon nano pipe array is with Fe (1nm)/Al
2O
3(10nm)/SiO
2/ Si uses typical chemical vapour deposition technique to synthesize in the quartz ampoule of tube furnace as catalyst.Al in the catalyst
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they deposit the film preparation of one deck nano thickness respectively on silicon chip by the electron beam evaporation deposition instrument.Adopt chemical vapour deposition technique, do carbon source with ethene, argon gas and hydrogen are having synthetic height-oriented carbon nano pipe array on the oxide layer Si substrate as carrier gas.The self assembly of carbon pipe can be with reference to existing bibliographical information in synthetic details and the fiber.
The second, the preparation of embedding stoste.
The prescription that embedding is used is classical " EPON 812 " prescription, and the present invention fills a prescription based on this, has increased an amount of flexibilizer.The method of concrete preparation is: at first, and configuration solution A and solution B.A liquid is by epoxy resin (SPI-Pon 812) and dodecenylsuccinic acid acid anhydride (DDSA) (60-65) by volume: 100 ratio is formed; B liquid is by epoxy resin (SPI-Pon 812) and methyl carbic anhydride (NMA) by volume 100: the ratio of (86-90) is formed.A liquid for preparing and B liquid made even dispersion in ultrasonic 10-30 minute in the ultrasonic cleaning machine the inside.Flexibilizer is the DT-2 type of buying from the southeast, Shenyang City chemical institute.Then with A liquid and B liquid with 2:8(A liquid: the volume ratio of B liquid=2:8) is mixed, the flexibilizer that adds A liquid and B liquid cumulative volume 8%--12% then, 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol (DMP-30) that adds cumulative volume at last, ultrasonic 10-30 minute, fully mix.Obtain embedding stoste at last.Array is put into the mould of embedding shape, injects embedding stoste then, in the polymerization case under the normal pressure 60 degrees centigrade solidified 36 hours, can obtain with the embedded carbon nano pipe array of epoxy resin.
The 3rd, the embedding sample is cut into slices.
Embedded sample is repaired, used the slicing machine of Lycra to cut into slices then, obtain the carbon nano-tube/polymer composite membrane of different-thickness.The thickness range of section is 50 nanometers to 100 micron.
The 4th, the battery assembling:
1, buckle type lithium-ion battery installation steps:
(1) earlier the battery stainless steel case is cleaned with distilled water, then, use the ultrasonic 20min of absolute ethyl alcohol again, 80 ℃ of oven dry in the baking oven with ultrasonic 20min in the distilled water ultrasonic cleaner.
Thick aligned carbon nanotube/the composite membrane of polymer of (2) 1～50um is a negative plate, in vacuum drying oven with before passed through the dry 80 ℃ of dryings of convection oven 6 hours.
(3) under the inert gas shielding environment, stainless steel casing, the carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, the lithium sheet, collector, the order of stainless steel cover installs.The middle electrolyte that drips makes electrolyte fully soak into electrode and diaphragm material.
(4) mounted lithium ion battery was positioned over the ventilation lucifugal placeization old about 24 hours.Use the timing point position method of electrochemical workstation CHI660 that the charge-discharge performance of battery is tested.
2, based on the making of aligned carbon nanotube/composite membrane of polymer as the polymer Li-ion battery of electrode material, concrete steps are as follows:
(1) aligned carbon nanotube/composite membrane of polymer of preparation battery product design size.
(2) cutting suitable dimension barrier film.
(3) the preparation battery is put well according to the order of positive pole/barrier film/negative pole/barrier film/positive pole or the order of negative pole/barrier film/positive pole/barrier film d, makes battery through coiling/lamination.
(4) be assembled into battery, and four edges seal after injecting electrolyte or sol-electrolyte.
(5) change into and place: charging changes at a slow speed, and after placing several weeks, filters out qualified products.
List of references
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Claims (7)
1. the preparation method of an aligned carbon nanotube/composite membrane of polymer is characterized in that concrete steps are as follows:
Carbon nano pipe array is immersed the mixed solution of epoxy monomer and flexibilizer, permeate embedding; Again in baking oven 55--65 ℃ solidified 12--40 hour, obtain embedded block; Be cut into the different-thickness compound foil with slicing machine, obtain the carbon nano-tube/polymer composite membrane, the thickness range of composite membrane is 50 nanometers to 50 micron.
2. the preparation method of aligned carbon nanotube/composite membrane of polymer according to claim 1 is characterized in that wherein the synthesis step of carbon nano-tube is:
Use structure to be Si/SiO
2/ Al
2O
3/ Fe is a catalyst, adopts chemical vapour deposition technique, does carbon source with ethene, as carrier gas, synthetic height-oriented carbon nano pipe array on the oxide layer Si substrate is being arranged with argon gas and hydrogen; The therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, growth 5-100 min in tube furnace; In the catalyst, SiO
2Thickness is 300-1000 μ m, Al
2O
3Thickness is 10-30 nm, and Fe thickness is 0.5-1.5 nm, Al
2O
3Be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they deposit the film preparation acquisition of one deck nano thickness respectively on silicon chip by the electron beam evaporation deposition instrument.
3. by the aligned carbon nanotube/composite membrane of polymer of the described method of claim 1 preparation.
4. aligned carbon nanotube/composite membrane of polymer as claimed in claim 2 is as the application of electrode material in the preparation lithium ion battery.
5. aligned carbon nanotube/composite membrane of polymer as claimed in claim 2 is as the application of senser in the preparation gas sensor.
6. application according to claim 4 is characterized in that described lithium ion battery is the buckle type lithium-ion battery,
Buckle type lithium-ion battery installation steps are:
(1) earlier the battery stainless steel case is cleaned with distilled water, then in ultrasonic cleaner, use distilled water ultrasonic 15--25 minute, use the ultrasonic 15--25 of absolute ethyl alcohol minute again, 75--85 ℃ of oven dry in baking oven at last;
(2) be negative plate with the thick aligned carbon nanotube/composite membrane of polymer of 1～50um, in the convection oven dry 75--86 ℃ dry 4-8 hour;
(3) under the inert gas shielding environment, according to stainless steel casing, the carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, the lithium sheet, collector, the order of stainless steel cover is installed; The middle electrolyte that drips makes electrolyte fully soak into electrode and diaphragm material;
(4) mounted lithium ion battery being positioned over the ventilation lucifugal place changed into more than 20 hours.
7. application according to claim 4 is characterized in that described lithium ion battery is a film lithium ion battery,
The film lithium ion battery installation steps are:
(1) aligned carbon nanotube/composite membrane of polymer of preparation battery product design size;
(2) cutting suitable dimension barrier film;
(3) the preparation battery is put well according to the order of positive pole/barrier film/negative pole/barrier film/positive pole or the order of negative pole/barrier film/positive pole/barrier film, makes battery through coiling/lamination;
(4) be assembled into battery, and four edges seal after injecting electrolyte or sol-electrolyte;
(5) change into and place: charging changes at a slow speed, and after placing several weeks, filters out qualified products.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593433A (en) * | 2012-02-27 | 2012-07-18 | 清华大学 | Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery |
| CN102983308A (en) * | 2012-12-17 | 2013-03-20 | 中国科学院上海硅酸盐研究所 | Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof |
| CN103647047A (en) * | 2013-12-23 | 2014-03-19 | 中国科学院上海硅酸盐研究所 | CNT (Carbon Nano Tube)/SnO2 coaxial composite array lithium ion battery negative electrode material |
| CN104701549A (en) * | 2013-12-06 | 2015-06-10 | 中国科学院上海高等研究院 | A carbon-free membrane electrode assembly |
| WO2016173127A1 (en) * | 2015-04-28 | 2016-11-03 | 南京工业大学 | Method for manufacturing vertically-growing open carbon nanotube thin film |
| US10195797B2 (en) | 2013-02-28 | 2019-02-05 | N12 Technologies, Inc. | Cartridge-based dispensing of nanostructure films |
| US10265683B2 (en) | 2006-05-19 | 2019-04-23 | Massachusetts Institute Of Technology | Continuous process for the production of nanostructures including nanotubes |
| US10350837B2 (en) | 2016-05-31 | 2019-07-16 | Massachusetts Institute Of Technology | Composite articles comprising non-linear elongated nanostructures and associated methods |
| US10399316B2 (en) | 2006-05-19 | 2019-09-03 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
| CN111341976A (en) * | 2020-03-17 | 2020-06-26 | 中航锂电技术研究院有限公司 | Electrolyte diaphragm, manufacturing method thereof and solid battery |
| CN112345592A (en) * | 2020-10-07 | 2021-02-09 | 大连理工大学 | Real-time monitoring method for optimized layout strain of loop-type measuring point of aircraft composite material key structure |
| US11031657B2 (en) | 2017-11-28 | 2021-06-08 | Massachusetts Institute Of Technology | Separators comprising elongated nanostructures and associated devices and methods, including devices and methods for energy storage and/or use |
| US11760848B2 (en) | 2017-09-15 | 2023-09-19 | Massachusetts Institute Of Technology | Low-defect fabrication of composite materials |
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