CN1172386C - Lithium-bearing composite nano carbon tube-graphite material and its preparing process - Google Patents
Lithium-bearing composite nano carbon tube-graphite material and its preparing process Download PDFInfo
- Publication number
- CN1172386C CN1172386C CNB021147035A CN02114703A CN1172386C CN 1172386 C CN1172386 C CN 1172386C CN B021147035 A CNB021147035 A CN B021147035A CN 02114703 A CN02114703 A CN 02114703A CN 1172386 C CN1172386 C CN 1172386C
- Authority
- CN
- China
- Prior art keywords
- tube
- carbon nano
- epoxy resin
- graphite
- lithium
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a preparation method for composite carbon nanometer tube-graphite lithium storage materials, which comprises steps: a carbon nanometer tube is added to epoxy resin; the materials are used for coating micron-sized graphite particles which are controlled for carbonation and graphitization. The materials prepared by the method of the present invention maintain various properties of the materials prepared by epoxy resin coating technology, and simultaneously, the lithium insertion volumetric capacity of the materials is greatly increased.
Description
Technical field
The present invention relates to chemical field,, the invention still further relates to the preparation method of lithium-bearing composite nano carbon tube-graphite material especially for the lithium-bearing composite nano carbon tube-graphite material of secondary cell.
Background technology
Lithium ion battery is current a kind of main flow secondary cell, has advantages such as specific energy height, memory-less effect.Because graphite has high removal lithium embedded capacity and the voltage characteristic smooth and low with respect to lithium metal, lithium ion battery is main at present to adopt compound between graphite layers as negative material.But graphite layers is maintained by Van der Waals force, adhesion a little less than, under the high current charge-discharge condition, powerful ion flow impacts and easily makes slippage between the aspect.This structural stability problem has restricted with the performance of compound between graphite layers as the lithium ion battery of negative material.The theoretical maximum insertion amount of lithium is LiC in the graphite
6, the respective electrical chemical capacity is 372mAh/g, both at home and abroad the capacity of negative pole graphite material general≤300mAh/g.Actual measurement Chuetsu Graphite WorksCO.Ltd. (OSAKA JAPAN) is 230mAh/g for the LF-18D graphite material capacity of used as negative electrode of Li-ion battery.Even such capacity still is apparent not enough for compact electric apparatus such as mobile phones, just more be difficult to bring into play the advantage of lithium ion battery in fields such as electric automobiles.Both at home and abroad just by changing the approach such as electronic state, crystal structure and surface texture of graphite, explore solution to the problems described above, for example in graphite cathode material, introduce nonmetalloid (boron, silicon, nitrogen, phosphorus, sulphur), metal and transition metal (potassium, aluminium, gallium and vanadium, nickel, cobalt, copper, iron), graphite particulate is carried out other processing (oxidation, formation superficial layer) etc.These methods cause all generally that preparation cost increases substantially, process complexity increases, but do not obtain the breakthrough of material property aspect.
Experiment showed, that the carbon nanometer micropore can store a large amount of lithium ions.But if directly use carbon nano-tube as negative material, the one, with high costs, the 2nd, the carbon nano-tube form is difficult to make fine and close battery electrode like cotton-wool.
Summary of the invention
The objective of the invention is to defective at the prior art existence, a kind of preparation method of lithium-bearing composite nano carbon tube-graphite material is provided, carbon nano-tube is combined with graphite with low cost, utilize the complementary structure characteristic of graphite and carbon nano-tube, the composite negative pole material of preparation from nanometer to the transition of micron particles surface smoothing.Because between the carbon nano-tube, all form the slit of nanometer scale between carbon nano-tube and the graphite particulate, the insert depth of lithium ion is little, process short, lithium ion not only can embed in the carbon nano-tube, and can embed between the carbon nano-tube and between carbon nano-tube and the graphite particulate, thereby can be reached for the purpose that lithium ion provides a large amount of embedded spaces position, increases substantially lithium ion battery charge/discharge capacity and current density.
Purpose of the present invention also relates to the lithium-bearing composite nano carbon tube-graphite material that method for preparing is provided.
The preparation method of lithium-bearing composite nano carbon tube-graphite material of the present invention comprises:
---in epoxy resin, add carbon nano-tube;
---above-mentioned material coats the micron order graphite granule;
---controlled carbonization;
---graphitization.
Described raw material epoxy resin: carbon nano-tube: the weight ratio of micron order graphite is 8～17: 0.1～0.6: 100.
Described epoxy resin can be E-44, E-50 or E-53.
Described carbon nano-tube, micron micro crystal graphite can be the commercial goods.
When in epoxy resin, adding carbon nano-tube, carbon nano-tube is evenly disperseed in epoxy resin.
Preferably coat and form the ball-type particulate, for this reason, can eliminate issuable bubble to 1300mPa.s～3600mPa.s and with defoamer with diluent adjustable ring epoxy resins viscosity.
During coating, can carry out granulation by spray drying.
Described diluent can be selected the dimethylbenzene or the ethylbenzene of the ethyl acetate of lipid or fourth lactones, arene.
Defoamer can be selected the sec-butyl alcohol or the n-butanol of lower alcohols, the amylalcohol of polar organic compounds class or dibutyl carbitol (DBC).
Carbonisation can be guaranteed the stable embedding of carbon nano-tube in unformed carbonization top layer.
Like this, with form the carbon nanoparticle on the top layer, the micron order graphite granule is the new construction that kernel, nano-micrometre particle seamlessly transit, thereby obtains the compound storage ion cathode material lithium of graphite-carbon nano-tube that capacitance is big, high-rate charge-discharge capability is good.
This patent compared with prior art, following advantage is arranged: 1, when retaining ring epoxy resins cladding process prepares every performance (comprising that coke layer with disordered structure prevents that graphite from inserting peeling off in the lithium process, lithium ion has good diffusion etc. in material) of material, the present invention increases substantially the slotting lithium capacity of material, and has improved the compatibility and the dynamic performance of carbon nano-tube and electrolyte solution; Owing to fully excavated cheap graphite material potentiality, prepared material price ratio height.Capacitance improves 120% o'clock cost and only improves 20% than pure graphite microparticles, 1/100 of not enough carbon nano-tube cost; 2, very complicated the external method of modifying (as middle phase microballoon graphitization).And this patent has realized making the technology of graphite particulate surface modification and making Nano surface one-time-reach-place with succinct technical route.
Embodiment
Embodiment 1 (in the 100kg micro crystal graphite)
1, epoxy resin is optional: E-44 epoxy resin, consumption 8.6kg;
2, dilution process and diluent are optional: ethyl acetate is as diluent, consumption 8.6kg;
Epoxy resin and diluent stir 15min jointly;
3, carbon nano-tube processing procedure and equipment are optional:
---consumption 0.1kg;
---with the catalyst based irregular carbon nano-tube of hollow, crimped that generates at 450 ℃ of cracking methane of Ni, caliber 10～25nm, pickling oven dry;
---with the carbon nano-tube dither mill preliminary treatment 6min of gained;
---carbon nano-tube is mixed the back with epoxy resin standby with the ultrasonic concussion of 35 ± 5Kh 5min;
4, graphite is optional: purity 99%, D
50=38 microns;
5, coating process and equipment are optional:
---the graphite after will handling in advance mixes stirring 30min with the epoxy resin of carbon nanotubes;
---said mixture is fed the standard spraying system carry out granulation and drying;
6, graphitizing process and equipment are optional:
---2800 ℃ of standard graphitizing furnaces;
---above-mentioned dry particles is handled 3h in graphitizing furnace, get finished product.
Embodiment 2 (in the 100kg micro crystal graphite)
1, epoxy resin is optional: E-53 epoxy resin, consumption 16kg;
2, dilution process and diluent are optional: ethyl acetate is as diluent, consumption 16kg; Epoxy resin and diluent stir 15min jointly;
3, carbon nano-tube processing procedure and equipment are optional:
---consumption 0.6kg;
---all the other are with embodiment 1
Embodiment 3 (in the 100kg micro crystal graphite)
1, epoxy resin is optional: E-50 epoxy resin, consumption 12kg;
2, dilution process and diluent are optional: ethyl acetate is as diluent, consumption 12kg; Epoxy resin and diluent stir 15min jointly;
3, carbon nano-tube processing procedure and equipment are optional:
---consumption 0.33kg;
---all the other are with embodiment 1
Claims (5)
1, the preparation method of a kind of carbon nano-tube-graphite composite lithium-bearing material is characterized in that comprising:
---adjust the concentration of epoxy resin with diluent, and add defoamer, in epoxy resin, add carbon nano-tube then;
---above-mentioned material coats the micron order graphite granule;
---controlled carbonization;
---graphitization;
The dimethylbenzene or the ethylbenzene of the ethyl acetate of described diluent selection lipid or fourth lactones, arene; Defoamer is selected sec-butyl alcohol, n-butanol, amylalcohol or dibutyl carbitol (DBC); Epoxy resin: carbon nano-tube: the weight ratio of micron order graphite is 8～17: 0.1～0.6: 100.
2, the preparation method of carbon nano-tube according to claim 1-graphite composite lithium-bearing material is characterized in that described epoxy resin is E-44, E-50 or E-53.
3, the preparation method of carbon nano-tube according to claim 1-graphite composite lithium-bearing material when it is characterized in that adding carbon nano-tube in epoxy resin, evenly disperses carbon nano-tube in epoxy resin.
4, the preparation method of carbon nano-tube according to claim 1-graphite composite lithium-bearing material is characterized in that with diluent adjustable ring epoxy resins viscosity to 1300mPas～3600mPas.
5, a kind of carbon nano-tube-graphite composite lithium-bearing material is characterized in that it being to be prepared by the described method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021147035A CN1172386C (en) | 2002-01-04 | 2002-01-04 | Lithium-bearing composite nano carbon tube-graphite material and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021147035A CN1172386C (en) | 2002-01-04 | 2002-01-04 | Lithium-bearing composite nano carbon tube-graphite material and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1373526A CN1373526A (en) | 2002-10-09 |
| CN1172386C true CN1172386C (en) | 2004-10-20 |
Family
ID=4743241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021147035A Expired - Fee Related CN1172386C (en) | 2002-01-04 | 2002-01-04 | Lithium-bearing composite nano carbon tube-graphite material and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172386C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4252847B2 (en) * | 2003-06-09 | 2009-04-08 | パナソニック株式会社 | Lithium ion secondary battery |
| CN100586843C (en) * | 2006-07-18 | 2010-02-03 | 中国科学院化学研究所 | Polymer inarching carbon nano-tube and method of manufacturing the same |
| CN102832378A (en) * | 2012-08-28 | 2012-12-19 | 浙江瓦力新能源科技有限公司 | Carbon anode material for lithium ion battery and preparation method for carbon anode material |
| CN103137954B (en) * | 2013-02-27 | 2015-05-20 | 扬州亚特尔新能源材料科技有限公司 | Novel carbon-carbon nanotube lithium ion battery cathode material and preparation method thereof |
| CN110854371A (en) * | 2019-11-26 | 2020-02-28 | 宁夏百川新材料有限公司 | Carbon composite negative electrode material and preparation method thereof |
-
2002
- 2002-01-04 CN CNB021147035A patent/CN1172386C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1373526A (en) | 2002-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen et al. | Rationally designed silicon nanostructures as anode material for lithium‐ion batteries | |
| JP5509458B2 (en) | Negative electrode material and manufacturing method thereof | |
| CN111653738B (en) | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof | |
| You et al. | Design strategies of Si/C composite anode for lithium‐ion batteries | |
| CN105098151A (en) | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof | |
| CN107845810A (en) | A kind of soft or hard carbon of lithium ion battery is modified the preparation method of negative material | |
| CN101064367A (en) | Compound material of anode fit for producing secondary battery and its produced battery | |
| CN108123111A (en) | A kind of lithium ion battery silicon substrate composite negative pole material, its preparation method and the negative electrode of lithium ion battery comprising the material | |
| Zou et al. | Microwave-assisted preparation of hollow porous carbon spheres and as anode of lithium-ion batteries | |
| CN1702893A (en) | Cathode material of Li-ion battery and preparation method, battery cathode, battery thereof | |
| WO2019019410A1 (en) | Modified lithium-free anode, method for preparing same, and lithium-ion battery comprising same | |
| CN1909268A (en) | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method | |
| CN107845797A (en) | A kind of lithium ion battery nano-silicone wire/carbon composite negative pole material and preparation method thereof | |
| WO2020211848A1 (en) | Nano-composite negative electrode material, preparation method therefor and use thereof | |
| CN113206249A (en) | Lithium battery silicon-oxygen composite negative electrode material with good electrochemical performance and preparation method thereof | |
| CN112952048A (en) | Silicon-carbon composite negative electrode material, preparation method thereof, electrode and secondary battery | |
| CN113690429A (en) | Carbon-coated graphene/metal oxide composite material and preparation method thereof | |
| CN1927707A (en) | Preparation method of artificial graphite charcoal negative electrode material and prepared artificial graphite charcoal negative electrode material | |
| CN1172386C (en) | Lithium-bearing composite nano carbon tube-graphite material and its preparing process | |
| CN111162254A (en) | Preparation method of silicon-carbon composite negative electrode material | |
| CN112670460B (en) | Silicon-carbon composite material, electrode, lithium ion battery, and preparation methods and applications thereof | |
| CN115458715A (en) | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN113422059B (en) | High-voltage carbon fluoride composite cathode material and preparation method thereof | |
| CN112670458B (en) | Preparation method and application of silicon-carbon material | |
| CN114361416A (en) | Silicon-based composite material, lithium ion battery and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |