CN102263221B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 57
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 54
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- 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 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 10
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- 238000002360 preparation method Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 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
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- 150000001875 compounds Chemical class 0.000 claims description 5
- -1 dodecenylsuccinic acid acid anhydride Chemical class 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
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- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 claims description 3
- 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
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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
- 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 nanotube/polymer composite membrane and its preparation method and application.
Background technology
The discovery of carbon nano-tube is a milestone in World Science history.Within 1991, Japanese Iijima finds carbon nano-tube (Carbon Nanotubes, 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, there are many potential using values, become the focus that people pay close attention to.Carbon nano-tube is widely studied to join prepares composite material in 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 in composite material, run through whole material.Utilize the order preparation of carbon nano pipe array to be uniformly dispersed, flexible carbon nano-tube/polymer composite material becomes new study hotspot.The method of 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 is being brought into play vital effect to human society Sustainable Development in Future, lithium ion battery is to develop in the 90's of last century, have specific energy high, have extended cycle life, security performance is good, memory-less effect, the advantage such as environmentally friendly, now be widely used in the portable electronics such as mobile phone, notebook computer, video camera, and be expected large-scale application in the storage of electric automobile and the clean electric energy such as solar energy, wind energy.Lithium ion battery is since commercialization, and electrode material is the study hotspot of field of batteries all the time.In the embedding lithium reaction of lithium ion battery, LiC6 was once considered to the highest composition of lithium carbon compound, but the report that surpasses theoretical capacity of nano-carbon material since 1994, allow people start 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 being rolled into by graphite linings.Carbon nano-tube has high surface area and excellent mechanical performance and electric property, since coming out, has been the focus of material science research field always.Research finds that the charge/discharge capacity of CNT (carbon nano-tube) can surpass the more than a times of graphite lithium intercalation compound theoretical capacity.But the random accumulation of carbon pipe is unfavorable for embedding lithium and de-embedding, how effectively bringing into play the effect of carbon pipe in lithium ion battery becomes a direction [4] [5] that is subject to extensive concern.
For 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.In kind electrode material, carbon pipe has kept the order of height, thereby has improved the conductivity of electrode material, and the two ends that all carbon Guan Jun remain on film are opening-like, is beneficial to improve storage lithium performance.Due to fixing of polymer, the electrode that carbon tube material is made has advantages of that the life-span is long, fail safe good, specific capacity is high, high rate performance is superior; By the composition in lithium ion battery applications and process optimization by this compound film electrode, 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, have again alignment carbon nano tube/polymer composite membrane of good flexibility and intensity and its preparation method and application.
The method of preparing alignment carbon nano tube/polymer composite membrane provided by the invention.Be mainly to classify raw material as with mixed solution and the carbon nano-pipe array of epoxy monomer and flexibilizer, by the method for infiltration, make resin monomer immerse array inner, then by the formation composite material that is heating and curing.Finally with slicing machine section, obtain carbon nanotube/polymer composite membrane.The innovation of the method is, has realized the making of vertical orientated carbon nano-tube film, and film upper and lower surface is connected by single-root carbon nano-tube, thereby brings into play better the electric property of carbon nano-tube.
The concrete steps of the inventive method are as follows:
The mixed solution that carbon nano pipe array is immersed to epoxy monomer and flexibilizer, permeates, embedding; 55--65 in baking oven again
oc solidifies 12--40 hour, obtains embedded block; With slicing machine, be cut into different-thickness compound foil, obtain carbon nanotube/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 epoxy resin, in the film obtaining after section, carbon nano-tube is completely equally distributed, and all perpendicular to the surface of film, therefore between film upper and lower surface, by a large amount of single-root carbon nano-tube UNICOMs, have very outstanding conductivity, film surface has a large amount of carbon nano-tube open end.
In the present invention, carbon nano pipe array can be prepared as follows:
The catalyst structure that 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 the film preparation that they deposit one deck nano thickness by electron beam evaporation deposition instrument respectively on silicon chip obtains; Adopt chemical vapour deposition technique, with ethene, do carbon source, using argon gas and hydrogen as carrier gas, having synthetic height-oriented carbon nano pipe array on oxide layer Si substrate; Therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, and 5-100 min grows in tube furnace.
The carbon nanotube/polymer composite membrane that said method prepares, can be used as electrode material, packs lithium ion battery into, preparation high-performance secondary lithium battery.Also this composite membrane can be prepared to gas sensor as senser, obtain high sensitivity, high stability, the Sensitive Apparatus of short recovery time.
One, fastening lithium ionic cell installation steps
(1) first battery stainless steel case is cleaned with distilled water, then in ultrasonic cleaner, use the ultrasonic 15--25 minute of distilled water, then use the ultrasonic 15--25 minute of absolute ethyl alcohol, finally 75--85 ℃ of oven dry in baking oven.
(2) with the thick alignment carbon nano tube/polymer composite membrane of 1～50um, be negative plate, dry 75--85 ℃ of dry 4--8 hour in convection oven.
(3) under inert gas shielding environment, according to stainless steel casing, carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, lithium sheet, collector, the order of stainless steel cover is installed.The middle electrolyte that drips, makes electrolyte fully infiltrate electrode and diaphragm material.
(4) mounted lithium ion battery being positioned over to ventilation lucifugal place changes into more than 20 hours.
Two, the making as the polymer Li-ion battery of electrode material based on alignment carbon nano tube/polymer composite membrane, concrete steps are as follows:
(1) prepare the alignment carbon nano tube/polymer composite membrane of battery product design size.
(2) cutting suitable dimension barrier film.
(3) prepare battery, according to the order of the order of positive pole/barrier film/negative pole/barrier film/positive pole or negative pole/barrier film/positive pole/barrier film, put well, through coiling/lamination, make battery.
(4) be assembled into battery, and inject four edge seals after electrolyte or sol-electrolyte.
(5) change into and place: charging changes at a slow speed, and places after several weeks, filters out qualified products.
Accompanying drawing explanation
Fig. 1, a is the pictorial diagram after resin embedding for carbon nano pipe array, figure b-f is that carbon nanotube/polymer composite membrane passes through multi-form aspect graph after crooked or folding.
Fig. 2, battery operated schematic diagram.
Fig. 3, fastening lithium ionic cell structure chart.
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 synthesizes with typical chemical vapour deposition technique in the quartz ampoule of tube furnace as catalyst.Al in catalyst
2o
3be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst, and they deposit respectively the film preparation of one deck nano thickness on silicon chip by electron beam evaporation deposition instrument.Adopt chemical vapour deposition technique, with ethene, do carbon source, argon gas and hydrogen, as carrier gas, are having synthetic height-oriented carbon nano pipe array on oxide layer Si substrate.In synthetic details and fiber, the self assembly of carbon pipe can be with reference to existing bibliographical information.
The second, the preparation of embedding stoste.
The formula that embedding is used is classical " EPON 812 " formula, and the present invention take that this fills a prescription as basis, has increased appropriate flexibilizer.The method of concrete preparation is: 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 forms; B liquid is by epoxy resin (SPI-Pon 812) and methyl carbic anhydride (NMA) by volume 100: the ratio of (86-90) forms.The A liquid preparing and B liquid make dispersed at ultrasonic cleaning machine the inside ultrasonic 10-30 minute.The DT-2 type that flexibilizer Shi Cong Shenyang City southeast chemical institute is bought.Then by A liquid and B liquid with 2:8(A liquid: volume ratio B liquid=2:8) is mixed, then the flexibilizer that adds A liquid and B liquid cumulative volume 8%--12%, 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol (DMP-30) that finally adds cumulative volume, ultrasonic 10-30 minute, fully mixes.Finally obtain embedding stoste.Array is put into the mould of embedding shape, is then injected embedding stoste, in polymerization case under normal pressure 60 degrees Celsius solidify 36 hours, can obtain with the good carbon nano pipe array of epoxy resin embedding.
The 3rd, embedding sample is cut into slices.
Embedded sample is repaired, then used the slicing machine of Lycra to cut into slices, obtain the carbon nanotube/polymer composite membrane of different-thickness.The thickness range of section is 50 nanometers to 100 micron.
The 4th, battery assembling:
1, fastening lithium ionic cell installation steps:
(1) first battery stainless steel case is cleaned with distilled water, then with ultrasonic 20min in distilled water ultrasonic cleaner, then use the ultrasonic 20min of absolute ethyl alcohol, 80 ℃ of oven dry in baking oven.
The thick alignment carbon nano tube/polymer composite membrane of (2) 1～50um is negative plate, in vacuum drying oven with before through convection oven dry 80 ℃ dry 6 hours.
(3) under inert gas shielding environment, stainless steel casing, carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, lithium sheet, collector, the order of stainless steel cover installs.The middle electrolyte that drips, makes electrolyte fully infiltrate electrode and diaphragm material.
(4) mounted lithium ion battery is positioned over to ventilation lucifugal placeization old about 24 hours.Use the timing point position method of electrochemical workstation CHI660 to test the charge-discharge performance of battery.
2, the making as the polymer Li-ion battery of electrode material based on alignment carbon nano tube/polymer composite membrane, concrete steps are as follows:
(1) prepare the alignment carbon nano tube/polymer composite membrane of battery product design size.
(2) cutting suitable dimension barrier film.
(3) prepare battery, according to the order of the order of positive pole/barrier film/negative pole/barrier film/positive pole or negative pole/barrier film/positive pole/barrier film d, put well, through coiling/lamination, make battery.
(4) be assembled into battery, and inject four edge seals after electrolyte or sol-electrolyte.
(5) change into and place: charging changes at a slow speed, and places after several weeks, filters out qualified products.
list of references
Claims (7)
1. a preparation method for alignment carbon nano tube/polymer composite membrane, is characterized in that concrete steps are as follows:
The mixed solution that carbon nano pipe array is immersed to epoxy monomer and flexibilizer, permeates, embedding; 55--65 ℃ of curing 12--40 hour in baking oven, obtains embedded block again; With slicing machine, be cut into different-thickness compound foil, obtain carbon nanotube/polymer composite membrane, the thickness range of composite membrane is 50 nanometers to 50 micron;
The compound method of described mixed solution is as follows:
First, configuration solution A and solution B; A liquid is by epoxy resin and dodecenylsuccinic acid acid anhydride (60-65) by volume: 100 ratio forms; B liquid is by epoxy resin and methyl carbic anhydride by volume 100: the ratio of (86-90) forms; The A liquid preparing and B liquid make dispersed at ultrasonic cleaning machine the inside ultrasonic 10-30 minute; Then A liquid and B liquid are mixed with the volume ratio of 2:8, then the flexibilizer that adds A liquid and B liquid cumulative volume 8%--12%, 1%～2% curing accelerator 2,4,6 three (dimethylamino methyl) phenol that finally adds cumulative volume, ultrasonic 10-30 minute, fully mixes; Finally obtain embedding stoste.
2. the preparation method of alignment carbon nano tube/polymer composite membrane according to claim 1, is characterized in that wherein the synthesis step of carbon nano-tube is:
Use structure is Si/SiO
2/ Al
2o
3/ Fe is catalyst, adopts chemical vapour deposition technique, with ethene, does carbon source, usings argon gas and hydrogen as carrier gas, is having synthetic height-oriented carbon nano pipe array on oxide layer Si substrate; Therein ethylene flow is 190-290 sccm, and argon flow amount is 400-620 sccm, and hydrogen flowing quantity is 20-48 sccm, and 5-100 min grows in tube furnace; In 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 the film preparation that they deposit one deck nano thickness by electron beam evaporation deposition instrument respectively on silicon chip obtains.
3. an alignment carbon nano tube/polymer composite membrane, it adopts preparation method's preparation as claimed in claim 1.
4. a lithium ion battery, it adopts alignment carbon nano tube/polymer composite membrane as claimed in claim 3 as electrode material.
5. a gas sensor, it adopts alignment carbon nano tube/polymer composite membrane as claimed in claim 3 as senser.
6. a kind of lithium ion battery as claimed in claim 4, is characterized in that described lithium ion battery is fastening lithium ionic cell,
Fastening lithium ionic cell installation steps are:
(1) first battery stainless steel case is cleaned with distilled water, then in ultrasonic cleaner, use the ultrasonic 15--25 minute of distilled water, then use the ultrasonic 15--25 minute of absolute ethyl alcohol, finally 75--85 ℃ of oven dry in baking oven;
(2) with the thick alignment carbon nano tube/polymer composite membrane of 1～50um, be negative plate, dry 75--86 ℃ of dry 4-8 hour in convection oven;
(3) under inert gas shielding environment, according to stainless steel casing, carbon nano tube/epoxy resin composite membrane, barrier film, waterleaf paper, lithium sheet, collector, the order of stainless steel cover is installed; The middle electrolyte that drips, makes electrolyte fully infiltrate electrode and diaphragm material;
(4) mounted lithium ion battery being positioned over to ventilation lucifugal place changes into more than 20 hours.
7. as according to a kind of lithium ion battery claimed in claim 4, it is characterized in that described lithium ion battery is film lithium ion battery,
Film lithium ion battery installation steps are:
(1) prepare the alignment carbon nano tube/polymer composite membrane of battery product design size;
(2) cutting suitable dimension barrier film;
(3) prepare battery, according to the order of the order of positive pole/barrier film/negative pole/barrier film/positive pole or negative pole/barrier film/positive pole/barrier film, put well, through coiling/lamination, make battery;
(4) be assembled into battery, and inject four edge seals after electrolyte or sol-electrolyte;
(5) change into and place: charging changes at a slow speed, and places after several weeks, filters out qualified products.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110170137.8A CN102263221B (en) | 2011-06-23 | 2011-06-23 | Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof |
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| CN201110170137.8A CN102263221B (en) | 2011-06-23 | 2011-06-23 | Oriented CNT (carbon nano tube)/polymer composite membrane as well as preparing method and application thereof |
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| US8337979B2 (en) | 2006-05-19 | 2012-12-25 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
| WO2008054541A2 (en) | 2006-05-19 | 2008-05-08 | Massachusetts Institute Of Technology | Nanostructure-reinforced composite articles and methods |
| CN102593433B (en) * | 2012-02-27 | 2014-08-13 | 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 |
| WO2014134484A1 (en) | 2013-02-28 | 2014-09-04 | N12 Technologies, Inc. | Cartridge-based dispensing of nanostructure films |
| CN104701549B (en) * | 2013-12-06 | 2017-02-22 | 中国科学院上海高等研究院 | A carbon-free membrane electrode assembly |
| 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 |
| CN104787748B (en) * | 2015-04-28 | 2016-11-02 | 南京工业大学 | Preparation method of vertically-grown open carbon nanotube film |
| US10350837B2 (en) | 2016-05-31 | 2019-07-16 | Massachusetts Institute Of Technology | Composite articles comprising non-linear elongated nanostructures and associated methods |
| WO2019055155A1 (en) | 2017-09-15 | 2019-03-21 | Massachusetts Institute Of Technology | Low-defect fabrication of composite materials |
| WO2019108616A1 (en) | 2017-11-28 | 2019-06-06 | Massachusetts Institute Of Technology | Separators comprising elongated nanostructures and associated devices and methods for energy storage and/or use |
| CN111341976B (en) * | 2020-03-17 | 2023-04-28 | 中创新航技术研究院(江苏)有限公司 | Electrolyte diaphragm, manufacturing method thereof and solid battery |
| CN112345592B (en) * | 2020-10-07 | 2022-02-18 | 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 |
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| CN102017246A (en) * | 2008-04-30 | 2011-04-13 | 住友电木株式会社 | Carbon material for negative electrode of lithium secondary battery, method for producing the same, negative electrode of lithium secondary battery and lithium secondary battery |
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| CN102017246A (en) * | 2008-04-30 | 2011-04-13 | 住友电木株式会社 | Carbon material for negative electrode of lithium secondary battery, method for producing the same, negative electrode of lithium secondary battery and lithium secondary battery |
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