CN100338796C - Process for modifying negative electrode material of lithium ion cell - Google Patents
Process for modifying negative electrode material of lithium ion cell Download PDFInfo
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- CN100338796C CN100338796C CNB2004100206068A CN200410020606A CN100338796C CN 100338796 C CN100338796 C CN 100338796C CN B2004100206068 A CNB2004100206068 A CN B2004100206068A CN 200410020606 A CN200410020606 A CN 200410020606A CN 100338796 C CN100338796 C CN 100338796C
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- negative material
- lithium ion
- ion battery
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- battery negative
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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 present invention relates to a method for modifying negative electrode material of a lithium ion battery. The negative electrode material is one-dimensional nanometer carbon material or a compound of the one-dimensional nanometer carbon material, carbon, tin bases and silica-based material, and the diameter range of the one-dimensional nanometer carbon material is between 1 nm to 500 nm. The present invention is characterized in that interval multiple covering of metal and nonmetal are carried out to negative electrode material surfaces, the metal uses stannum, copper, silver and chromium, and the nonmetal uses carbon, silicon and boron. The modification to the negative electrode material of a lithium ion battery by the method of the present invention improves lithium storing capacity, cycle performance and dynamic performance of negative electrodes of the lithium ion battery.
Description
Technical field:
The inventive method relates to the method for modifying of lithium ion battery negative material, and the inventive method provides the performance of the method improvement lithium ion battery negative material of a kind of interval multilayer coating especially.
Background technology:
Lithium ion battery is a kind of new and effective chemical power source, is widely used in the supporting power supply of portable type electronic product.Even along with the improvement of material technology progress and battery design, the range of application of lithium ion battery is expected further to be extended to from information industry fields such as energy traffic, space flight and aviation, national defence.This has also proposed requirements at the higher level to performances such as useful life of lithium ion battery, discharge-rates.The raising of lithium ion battery performance is decided by the improvement of negative material performance and specific capacity to a great extent.
Nano carbon tube and nanofiber are the carbon nano-materials with accurate one-dimentional structure, have characteristics such as draw ratio is big, specific strength is high, conduct electricity very well, chemical stability is good.Nano carbon fiber/nano carbon tube both can be used as lithium ion battery negative separately, also can add other negative materials composition composite negative pole materials by certain proportion.
The inventive method has proposed the spaced surface coating modification method of a kind of nano carbon tube/nano carbon fiber ion cathode material lithium or nano carbon tube/nano carbon fiber composite lithium ion battery cathode, has characteristics such as significantly improving its lithium storage content, cycle characteristics, dynamic performance.
Summary of the invention:
The purpose of the method for the present invention is that improves lithium storage content, cycle characteristics, the dynamic performance of lithium ion battery by the modification lithium-ion battery negative material.
The inventive method provides a kind of method of modifying of lithium ion battery negative material, negative material is the compound of nano carbon material in one dimension or nano carbon material in one dimension and carbonaceous, tinbase, silica-base material, the diameter range of nano carbon material in one dimension is between 1nm-500nm, it is characterized in that: the anticathode material surface carries out metal and nonmetal interval multilayer coats processing, metal adopts tin, copper, silver, chromium, nonmetal employing carbon, silicon, boron.
The method of modifying of lithium ion battery negative material, ground floor clad metal on described negative material has tin, copper, silver, chromium.
The method of modifying of lithium ion battery negative material, the method for ground floor clad metal is a chemical plating on described negative material.
The method of modifying of lithium ion battery negative material, the second layer coats nonmetally on described negative material, and carbon, silicon, boron are arranged
The method of modifying of lithium ion battery negative material, the second layer coats nonmetallic method on described negative material has chemical vapour deposition (CVD), earlier coats presoma two kinds of high-temperature process again.
The method of modifying of lithium ion battery negative material, described chemical plating method be the anticathode material under the oxidation of potassium bichromate, potassium permanganate or thiosulfate, after stannic chloride and palladium bichloride sensitization and activation, in copper sulphate or liquor argenti nitratis ophthalmicus, electroplate respectively.
The method of modifying of lithium ion battery negative material, described chemical vapor deposition process is to be carbon source with the hydrocarbon, and being the silicon source in 600-800 torr pressure and 800-1200 ℃ of temperature or with the silane compound carries out deposition processes under 600-800 torr pressure and 500-800 ℃.
The method of modifying of lithium ion battery negative material, described first covering liquid phase presoma high-temperature process again are that negative material and pitch, mixed with resin is even, handle 3-6 hour under inert atmosphere and 900-1200 ℃ of condition.
The inventive method has improved lithium storage content, cycle characteristics, the dynamic performance of lithium ion battery negative to the modification of lithium ion battery negative material.
Embodiment:
Embodiment 1:
The at first oxidation 1 hour in potassium bichromate solution of the nano carbon fiber of selecting average diameter 150nm for use respectively at sensitization and activation in stannic chloride and the palladium chloride solution, is electroplated in copper-bath more afterwards, obtains the nano carbon fiber negative material that the surface coats copper; With itself and hard pitch evenly mix the back under argon gas atmosphere 1100 ℃ handled 3 hours, obtain the nano carbon fiber negative material that the surface coats copper and carbon-coating.Lithium ion battery negative evaluation method testing result is routinely: capacity improves 10% behind 500 cycle charge-discharges, and capacity improves 30% first, and efficient remains unchanged first.
Embodiment 2:
The at first oxidation 1 hour in potassium bichromate solution of the nano carbon fiber of selecting average diameter 250nm for use respectively at sensitization and activation in stannic chloride and the palladium chloride solution, is electroplated in liquor argenti nitratis ophthalmicus more afterwards, obtains the nano carbon fiber negative material of coated with silver on surface; With propane be carbon source 1000 ℃ of following chemical vapour deposition (CVD)s 2 hours, obtain the nano carbon fiber negative material of coated with silver on surface and carbon-coating.Lithium ion battery negative evaluation method testing result is routinely: capacity improves 15% behind 500 cycle charge-discharges, and capacity improves 35% first, and efficient remains unchanged first.
Embodiment 3:
The at first oxidation 1 hour in potassium bichromate solution of nano carbon tube (10wt%)/MCMB composite negative pole material of selecting average diameter 90nm for use, again respectively at sensitization and activation in stannic chloride and the palladium chloride solution, in liquor argenti nitratis ophthalmicus, electroplate afterwards, obtain the composite negative pole material that the surface coats copper; With propane be carbon source 1000 ℃ of following chemical vapour deposition (CVD)s 2 hours, obtain the composite negative pole material that the surface coats copper and carbon-coating.Lithium ion battery negative evaluation method testing result is routinely: capacity improves 18% behind 500 cycle charge-discharges, and capacity improves 30% first, and efficient remains unchanged first.
Embodiment 4:
Select nano carbon fiber (weight ratio 8%)/native graphite composite negative pole material of average diameter 200nm for use, at first oxidation 1 hour in potassium bichromate solution, again respectively at sensitization and activation in stannic chloride and the palladium chloride solution, in liquor argenti nitratis ophthalmicus, electroplate afterwards, obtain the composite negative pole material of coated with silver on surface; With itself and hard pitch evenly mix the back under argon gas atmosphere 1100 ℃ handle the composite negative pole obtained coated with silver on surface and carbon-coating in 3 hours.Lithium ion battery negative evaluation method testing result is routinely: capacity improves 20% behind 500 cycle charge-discharges, and capacity improves 20% first, and efficient remains unchanged first.
Claims (8)
1, a kind of method of modifying of lithium ion battery negative material, negative material is the compound of nano carbon material in one dimension or nano carbon material in one dimension and carbonaceous, tinbase, silica-base material, the diameter range of nano carbon material in one dimension is between 1nm-500nm, it is characterized in that: the anticathode material surface carries out metal and nonmetal interval multilayer coats processing, metal adopts a kind of of tin, copper, silver, chromium, nonmetal employing carbon, silicon, boron a kind of.
2, according to the method for modifying of the described lithium ion battery negative material of claim 1, it is characterized in that: the ground floor clad metal has a kind of of tin, copper, silver, chromium on described negative material.
3, according to the method for modifying of the described lithium ion battery negative material of claim 2, it is characterized in that: the method for ground floor clad metal is a chemical plating on described negative material.
4, according to the method for modifying of the described lithium ion battery negative material of claim 2, it is characterized in that: on described negative material the second layer coat nonmetal, carbon, silicon, boron a kind of.
5, according to the method for modifying of the described lithium ion battery negative material of claim 4, it is characterized in that: the second layer coats nonmetallic method on described negative material chemical vapour deposition (CVD) or first covering liquid phase presoma two kinds of high-temperature process again.
6, according to the method for modifying of the described lithium ion battery negative material of claim 3, it is characterized in that: described chemical plating method is negative material oxidation in potassium bichromate, potassium permanganate or thiosulfate solution, through stannic chloride sensitization and palladium bichloride activation, in copper sulphate or liquor argenti nitratis ophthalmicus, electroplate at last again.
7, according to the method for modifying of the described lithium ion battery negative material of claim 5, it is characterized in that: described chemical chemical vapor deposition process is to be carbon source with the hydrocarbon, and being the silicon source in 600-800 torr pressure and 800-1200 ℃ of temperature or with the silane compound carries out deposition processes under 600-800 torr pressure and 500-800 ℃.
8, according to the method for modifying of the described lithium ion battery negative material of claim 5, it is characterized in that: described first covering liquid phase presoma high-temperature process again is that negative material and pitch, mixed with resin is even, handles 3-6 hour under inert atmosphere and 900-1200 ℃ of condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100206068A CN100338796C (en) | 2004-05-26 | 2004-05-26 | Process for modifying negative electrode material of lithium ion cell |
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| CNB2004100206068A CN100338796C (en) | 2004-05-26 | 2004-05-26 | Process for modifying negative electrode material of lithium ion cell |
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| CN1705148A CN1705148A (en) | 2005-12-07 |
| CN100338796C true CN100338796C (en) | 2007-09-19 |
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| US20100285358A1 (en) | 2009-05-07 | 2010-11-11 | Amprius, Inc. | Electrode Including Nanostructures for Rechargeable Cells |
| CN101626075B (en) * | 2009-08-03 | 2011-03-30 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| KR20120102680A (en) | 2009-11-11 | 2012-09-18 | 암프리우스, 인코포레이티드 | Intermediate layers for electrode fabrication |
| CN102122708A (en) * | 2010-01-08 | 2011-07-13 | 中国科学院物理研究所 | Negative pole material for lithium-ion secondary battery, negative pole containing negative pole material, preparation method of negative pole and battery containing negative pole |
| US9780365B2 (en) | 2010-03-03 | 2017-10-03 | Amprius, Inc. | High-capacity electrodes with active material coatings on multilayered nanostructured templates |
| CN102844917B (en) | 2010-03-03 | 2015-11-25 | 安普雷斯股份有限公司 | For the template electric electrode structure of position activity material |
| US9172088B2 (en) | 2010-05-24 | 2015-10-27 | Amprius, Inc. | Multidimensional electrochemically active structures for battery electrodes |
| CN101986442A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | Lithium ion battery cathode material containing three-dimensional conductive structure and preparation method thereof |
| CN102479948B (en) | 2010-11-30 | 2015-12-02 | 比亚迪股份有限公司 | Negative active core-shell material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery |
| CN102185142A (en) * | 2011-04-08 | 2011-09-14 | 厦门大学 | Composite carbon cathode material for lithium ion battery and preparation method thereof |
| EP2727175A4 (en) | 2011-07-01 | 2015-07-01 | Amprius Inc | Template electrode structures with enhanced adhesion characteristics |
| CN102324508A (en) * | 2011-09-14 | 2012-01-18 | 耿世达 | The alloy that three-dimensional conductive structure is contained in a kind of inside coats negative material and preparation method thereof |
| TWI689126B (en) | 2014-05-12 | 2020-03-21 | 美商安普雷斯公司 | Structurally controlled deposition of silicon onto nanowires |
| CN105098163B (en) * | 2014-05-16 | 2017-09-29 | 微宏动力***（湖州）有限公司 | A kind of preparation method of cladded type electrode material |
| TWI565654B (en) | 2014-08-08 | 2017-01-11 | Kureha Corp | Production method of carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery and carbonaceous material for negative electrode of nonaqueous electrolyte secondary battery |
| TWI599092B (en) | 2014-08-08 | 2017-09-11 | Kureha Corp | Non-Aqueous Electrolyte Secondary Battery Negative Carbonaceous Material |
| TWI604655B (en) | 2014-08-08 | 2017-11-01 | Kureha Corp | Non-aqueous electrolyte secondary battery negative carbonaceous material |
| CN105140480A (en) * | 2015-08-07 | 2015-12-09 | 田东 | Preparation method of high-capacity tin-carbon anode material |
| CN107093710B (en) * | 2017-03-31 | 2019-10-08 | 宁夏博尔特科技有限公司 | Two-coat lithium ion battery negative material and preparation method thereof and lithium ion battery |
| CN108206285B (en) * | 2017-12-12 | 2021-08-24 | 中国科学院物理研究所 | Composite coated nano tin anode material and preparation method and application thereof |
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| CN1347389A (en) * | 1999-03-01 | 2002-05-01 | 北卡罗来纳-查佩尔山大学 | Nanotube-based high energy material and method |
| US20030152835A1 (en) * | 2002-02-08 | 2003-08-14 | Sankar Dasgupta | Carbon fibre containing negative electrode for lithium battery |
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- 2004-05-26 CN CNB2004100206068A patent/CN100338796C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1347389A (en) * | 1999-03-01 | 2002-05-01 | 北卡罗来纳-查佩尔山大学 | Nanotube-based high energy material and method |
| US6422450B1 (en) * | 1999-03-01 | 2002-07-23 | University Of North Carolina, The Chapel | Nanotube-based high energy material and method |
| US20030152835A1 (en) * | 2002-02-08 | 2003-08-14 | Sankar Dasgupta | Carbon fibre containing negative electrode for lithium battery |
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