CN102299330A - Active carbon-nano silicon composite powder, synthetic method thereof and lithium ion battery prepared therefrom - Google Patents
Active carbon-nano silicon composite powder, synthetic method thereof and lithium ion battery prepared therefrom Download PDFInfo
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- CN102299330A CN102299330A CN2011101923833A CN201110192383A CN102299330A CN 102299330 A CN102299330 A CN 102299330A CN 2011101923833 A CN2011101923833 A CN 2011101923833A CN 201110192383 A CN201110192383 A CN 201110192383A CN 102299330 A CN102299330 A CN 102299330A
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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
Abstract
The invention relates to a nano silicon composite graphite material with a high charge-discharge efficiency and good cycle performance and a synthetic method thereof, and a battery prepared from the material and a commercialized anode electrolyte system. Porous active carbon material and a nano silicon simple substance material are treated with a high energy ball milling, and then are cladded by asphalt or a polymer material in order to inlay the nano silicon material into the active carbon apertures; therefore, an active carbon-nano silicon composite powder with good conductivity and stable charge and discharge performance is obtained. The invention also relates to a lithium ion battery prepared from the active carbon-nano silicon composite powder.
Description
Technical field
The lithium ion battery that the present invention relates to a kind of negative electrode active material and adopt this negative electrode active material to make particularly relates to the lithium ion battery of a kind of activated carbon-nano-silicon composite granule and synthetic method and making thereof.
Background technology
Lithium rechargeable battery is described as the high-performance " green energy resource " of 21 century, have application fields and vast market prospect, compare other chemical power source, the monomer battery voltage height is arranged, in light weight, energy density and specific energy height, self-discharge rate is low, have extended cycle life advantage such as memory-less effect and security performance are good.Therefore, little of digital product, all obtain using more widely to power vehicle greatly.No matter in which application, how giving full play to the light advantage of lithium ion battery, is the problem of developing material technical staff and lithium ion battery manufacturing technology personnel research.
The present business-like graphite-like negative pole that is mainly, the graphite-like negative material has capacity height, cheap, the abundant advantage of originating, but now can't satisfy the requirement of lithium ion battery, limit its extensive use in lithium ion battery to a certain extent material capacity density.
Because the feature embedding lithium capacity that aluminosilicate alloy material is high, aluminosilicate alloy material has obtained greatly paying attention in recent years, but the conductance of silicon materials is relatively poor, discharge and recharge defectives such as efflorescence, brought that efficient is low first, discharge and recharge problems such as decay is fast, the synthetic cost of aluminosilicate alloy material is higher simultaneously, has also had a strong impact on the progress of its industrialization.
Summary of the invention
For solving the problems of the technologies described above, the invention provides and a kind ofly have height and charge and discharge efficient, the nano-silicon composite graphite material and the synthetic method thereof of good cycle, and made battery with its business-like anodal electrolyte system of arranging in pairs or groups.
Synthetic method disclosed by the invention is: the active carbon material of usefulness porous and the elementary silicon material of nanometer are through high-energy ball milling, and then adopt pitch or high polymer material to coat, silicon nano material is resided in the activated carbon hole, obtain a kind of good conductivity, discharge and recharge the activated carbon-nano-silicon composite granule of stable external coating, its concrete steps comprise:
(1) active carbon particle of porous behind mechanical forcing crushing, through separator, obtains 900 purpose active carbon particle powders with impact grinder under fan action;
(2) the active carbon particle powder after the sorting is carried out simple and mechanical the mixing with nano-silicon simple substance material, change high energy ball mill then over to and mix by force;
(3) in strong mixed compound, divide to add pitch for three times or high polymer material wraps up, add then and continue ball milling in the ball mill;
(4) mixed powder that three kinds of powder are formed is being warmed up under the protection of inert atmosphere about the 800-1100 degree, keeps cooling after 6-12 hour;
(6) cooled product obtains activated carbon-nano-silicon composite granule through broken classification.
Described active carbon particle powder, the mass ratio of nano-silicon simple substance material and pitch or high polymer material are 1: 0.5: 1-8: 3: 1.
The invention also discloses synthetic according to the method described above activated carbon-nano-silicon composite granule.Described activated carbon-nano-silicon composite granule is with after Delanium or natural modified graphite mix, as the negative electrode active material of lithium rechargeable battery.Perhaps, described activated carbon-nano-silicon composite granule mixes with the native graphite of Delanium presoma or spheroidization, adopt again pitch or high polymer material secondary the parcel sintering after, as the active material of lithium ion secondary battery negative pole.Described activated carbon-nano-silicon composite granule shared mass percent in secondary parcel sinter is 6-10%.
The invention also discloses a kind of lithium ion battery that adopts described activated carbon-nano-silicon composite granule to make, when negative pole mixes slurry, add described activated carbon-nano-silicon composite granule.The mass percent that described activated carbon-nano-silicon composite granule or the described secondary parcel sinter that contains activated carbon-nano-silicon composite granule account for battery cathode is 6-100%.
In sum, this patent has been invented a kind of synthetic method of passing through the composite action stable silicon nano particle of fine active carbon granule and pitch-coating, and prepare the compound powder body material of silicon-carbon by this method, adopt this powder body material the capacity of negative plates of lithium ion battery to be improved and have a clear superiority in as active material.
Description of drawings
Fig. 1 is the performance chart of the embodiment of the invention 5.
Embodiment
Embodiments of the invention comprise following steps:
1, select the active carbon particle of porous for use, with impact grinder through behind the mechanical forcing crushing under fan action machine by analysis, obtain 900 purpose powders;
2,, through simple and mechanical mixing, change high energy ball mill then over to and mix by force with certain mass ratio with active carbon particle after the sorting and nano-silicon simple substance material;
3, in strong mixed compound, divide and add a certain proportion of pitch for three times and add in the ball mill and continue ball milling;
4, the mixed powder that three kinds of powder are formed is being warmed up under the protection of inert atmosphere about 800～1100 degree by certain programming rate, keeps cooling after 6～12 hours.
5, cooled product obtains compound silicon nano-graphite negative material through broken classification.The using method of this composite granule can be further mixed with the native graphite of Delanium presoma (as petroleum coke, coal tar etc.) or spheroidization, adopts pitch or high polymer to carry out secondary and coats sintering and obtain the lithium ion battery composite material.Also can directly this composite granule directly be mixed use with business-like Delanium or natural modified graphite, use as active material for negative pole of Li-ion secondary battery.
6, lithium secondary battery finished product battery adopts traditional 053450 aluminum hull model, adopts common processes condition in the industry, through mixing slurry, and coating, film-making, assembling, fluid injection such as changes at operation, the just very LiCoO of collocation
2
Electrolyte is EC: EMC: DEC=1: 1: 1 (1M lithium salt), and when negative pole mixes slurry, add a certain proportion of this comprehensive silicon nano-graphite negative material and use as active material.
Described nano-silicon simple substance material selection commercialization silica flour.
Table 1:
Illustrate:
Activated carbon: silica flour: the pitch ratio is meant mixing quality ratio in the building-up process.
No secondary coats and is meant directly with activated carbon: silica flour: pitch is when the use of part active material.
Having secondary to coat is meant activated carbon: silica flour: the pitch composite powder is with certain proportion and coating again after the graphite presoma mixes.
Accounting was the composite powder accounting during secondary coated.
Account for the negative electrode active material ratio and be meant composite powder (once or secondary coat) addition as active material in batching.
Negative electrode active material is made of jointly composite powder and certain commercialization Delanium in embodiment and the Comparative Examples, and what all embodiment and Comparative Examples were used is Delanium of the same race.
As seen, embodiment 1,5,6 relative Comparative Examples, and capacity of negative plates is improved, and efficient is also better first
Claims (8)
1. the synthetic method of activated carbon-nano-silicon composite granule, its step comprises:
(1) active carbon particle of porous behind mechanical forcing crushing, through separator, obtains 900 purpose active carbon particle powders with impact grinder under fan action;
(2) the active carbon particle powder after the sorting is carried out simple and mechanical the mixing with nano-silicon simple substance material, change high energy ball mill then over to and mix by force;
(3) in strong mixed compound, divide to add pitch for three times or high polymer material wraps up, add then and continue ball milling in the ball mill;
(4) mixed powder that three kinds of powder are formed is being warmed up under the protection of inert atmosphere about the 800-1100 degree, keeps cooling after 6-12 hour;
(6) cooled product obtains activated carbon-nano-silicon composite granule through broken classification.
2. synthetic method as claimed in claim 1 is characterized in that, active carbon particle powder, the mass ratio of nano-silicon simple substance material and pitch or high polymer material are 1: 0.5: 1-8: 3: 1.
3. activated carbon-nano-silicon composite granule synthetic as method as described in the claim 1-2.
4. activated carbon as claimed in claim 3-nano-silicon composite granule is characterized in that, described activated carbon-nano-silicon composite granule is with after Delanium or natural modified graphite mix, as the negative electrode active material of lithium rechargeable battery.
5. activated carbon as claimed in claim 3-nano-silicon composite granule, it is characterized in that, described activated carbon-nano-silicon composite granule mixes with the native graphite of Delanium presoma or spheroidization, after adopting pitch or high polymer material secondary parcel sintering again, as the active material of lithium ion secondary battery negative pole.
6. activated carbon as claimed in claim 5-nano-silicon composite granule is characterized in that, described activated carbon-nano-silicon composite granule shared mass percent in secondary parcel sinter is 6-10%.
7. a lithium ion battery that adopts the described activated carbon of claim 3-6-nano-silicon composite granule to make is characterized in that, when the negative pole of described lithium ion mixes slurry, adds described activated carbon-nano-silicon composite granule.
8. lithium ion battery as claimed in claim 7 is characterized in that, the mass percent that described activated carbon-nano-silicon composite granule or the described secondary parcel sinter that contains activated carbon-nano-silicon composite granule account for battery cathode is 6-100%.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840140A (en) * | 2012-11-21 | 2014-06-04 | 清华大学 | Porous carbon silicon composite material and preparation method thereof |
| CN106129522A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method utilizing lithium ion battery negative to reclaim graphite |
| CN106229479A (en) * | 2016-08-18 | 2016-12-14 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery activated carbon composite negative pole material, preparation method and lithium ion battery |
| CN106784759A (en) * | 2017-04-01 | 2017-05-31 | 重庆大学 | A kind of silicon/activated carbon composite negative pole material and preparation method thereof |
| CN107017384A (en) * | 2016-01-27 | 2017-08-04 | 陕西煤业化工技术研究院有限责任公司 | A kind of preparation method of silicon-carbon composite cathode material |
| CN108701809A (en) * | 2016-02-17 | 2018-10-23 | 瓦克化学股份公司 | The method for preparing Si/C composite particles |
| CN108878776A (en) * | 2018-07-17 | 2018-11-23 | 四川聚能仁和新材料有限公司 | A kind of battery cathode sheet and preparation method thereof and a kind of battery |
| CN108963226A (en) * | 2018-07-17 | 2018-12-07 | 四川聚能仁和新材料有限公司 | C silicon/activity silicon/charcoal core-shell structure composite negative pole material and preparation method thereof |
| CN109346681A (en) * | 2018-08-17 | 2019-02-15 | 福建翔丰华新能源材料有限公司 | A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof |
| CN111348647A (en) * | 2020-03-16 | 2020-06-30 | 西安越遴新材料研究院有限公司 | Silicon-carbon composite material with multi-layer coating structure and preparation method thereof |
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| CN101108918A (en) * | 2007-08-16 | 2008-01-23 | 湛江市新蓄能源科技有限公司 | High softening point bitumen used as lithium ion battery negative pole coating layer material and manufacture thereof |
| CN101244814A (en) * | 2007-02-13 | 2008-08-20 | 深圳市比克电池有限公司 | Method for producing lithium cell silicon carbon negative pole material and produced silicon carbon negative pole material |
| CN101339987A (en) * | 2008-07-21 | 2009-01-07 | 长沙市海容电子材料有限公司 | Silicon-carbon composite cathode material of lithium ion battery and preparation thereof |
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| CN101244814A (en) * | 2007-02-13 | 2008-08-20 | 深圳市比克电池有限公司 | Method for producing lithium cell silicon carbon negative pole material and produced silicon carbon negative pole material |
| CN101108918A (en) * | 2007-08-16 | 2008-01-23 | 湛江市新蓄能源科技有限公司 | High softening point bitumen used as lithium ion battery negative pole coating layer material and manufacture thereof |
| CN101339987A (en) * | 2008-07-21 | 2009-01-07 | 长沙市海容电子材料有限公司 | Silicon-carbon composite cathode material of lithium ion battery and preparation thereof |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103840140A (en) * | 2012-11-21 | 2014-06-04 | 清华大学 | Porous carbon silicon composite material and preparation method thereof |
| CN103840140B (en) * | 2012-11-21 | 2017-12-26 | 清华大学 | porous carbon-silicon composite material and preparation method thereof |
| CN107017384A (en) * | 2016-01-27 | 2017-08-04 | 陕西煤业化工技术研究院有限责任公司 | A kind of preparation method of silicon-carbon composite cathode material |
| CN108701809A (en) * | 2016-02-17 | 2018-10-23 | 瓦克化学股份公司 | The method for preparing Si/C composite particles |
| CN108701809B (en) * | 2016-02-17 | 2021-11-09 | 瓦克化学股份公司 | Method for producing Si/C composite particles |
| CN106229479B (en) * | 2016-08-18 | 2019-10-18 | 惠州市鼎元新能源科技有限公司 | A kind of lithium ion battery active carbon composite negative pole material, preparation method and lithium ion battery |
| CN106229479A (en) * | 2016-08-18 | 2016-12-14 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery activated carbon composite negative pole material, preparation method and lithium ion battery |
| CN106129522A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method utilizing lithium ion battery negative to reclaim graphite |
| CN106784759A (en) * | 2017-04-01 | 2017-05-31 | 重庆大学 | A kind of silicon/activated carbon composite negative pole material and preparation method thereof |
| CN108963226A (en) * | 2018-07-17 | 2018-12-07 | 四川聚能仁和新材料有限公司 | C silicon/activity silicon/charcoal core-shell structure composite negative pole material and preparation method thereof |
| CN108878776B (en) * | 2018-07-17 | 2021-03-09 | 四川聚能仁和新材料有限公司 | Battery negative plate and preparation method thereof, and battery |
| CN108878776A (en) * | 2018-07-17 | 2018-11-23 | 四川聚能仁和新材料有限公司 | A kind of battery cathode sheet and preparation method thereof and a kind of battery |
| CN109346681A (en) * | 2018-08-17 | 2019-02-15 | 福建翔丰华新能源材料有限公司 | A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof |
| CN111348647A (en) * | 2020-03-16 | 2020-06-30 | 西安越遴新材料研究院有限公司 | Silicon-carbon composite material with multi-layer coating structure and preparation method thereof |
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Application publication date: 20111228 |