CN102779984A - Carbon-cladded nanometer tin particle composite negative electrode material and preparation method thereof - Google Patents
Carbon-cladded nanometer tin particle composite negative electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN102779984A CN102779984A CN2011101187986A CN201110118798A CN102779984A CN 102779984 A CN102779984 A CN 102779984A CN 2011101187986 A CN2011101187986 A CN 2011101187986A CN 201110118798 A CN201110118798 A CN 201110118798A CN 102779984 A CN102779984 A CN 102779984A
- Authority
- CN
- China
- Prior art keywords
- carbon
- tin particles
- composite negative
- negative pole
- coated nano
- 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.)
- Pending
Links
Images
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
Abstract
The invention provides a negative electrode material of a lithium ion battery and a preparation method thereof. The negative electrode material is composed of a carbon-cladded nanometer tin particle composite in a three dimensional network structure, and tin particles are uniformly dispersed and have a particle size of 3 to 5 nm. The electrode made of the composite has high reversible capacity and good cycling stability. Furthermore, the preparation method provided in the invention has the advantages of a simple process, strong controllability, low cost and environment friendliness.
Description
Technical field
The present invention relates to the lithium ion battery negative material field, particularly a kind of carbon-coated nano tin particles composite negative pole material and preparation method.
Background technology
Lithium ion battery becomes current internationally recognized desirable chemical energy source owing to have outstanding advantages such as operating voltage height, specific energy are high, capacity is big, volume is little, pollution-free; Be widely used in electronic products such as mobile phone, laptop computer, bigger development space will be brought to lithium ion battery in the electric automobile field that enlarges day by day.
The chemical property of lithium ion battery depends primarily on the structure and the performance of electrode used therein material and electrolyte, and negative material is one of key that influences the lithium ion battery performance.Wherein, tin is owing to have high theoretical capacity (Sn:991mAhg
-1), caused many research workers' interest.But tin produces bigger volumetric expansion in charge and discharge process, the internal stress of material is very big, causes the peeling off of electrode material, efflorescence and destruction easily, thereby shows relatively poor cycle performance.At present, improving one of the tin cycle performance effective method is exactly that tin particles with nanoscale is scattered in the carbon base body.But the fusing point of tin low (232 ℃), preparation nanoscale tin particles is dispersed in and is still a difficult point in the carbon base body.Generally select for use alloy or its compound of having prepared to do main body, form the coating layer of carbon containing again in body surfaces.Like Zhang etc., at first utilize SiO
2Be template, Na
2SnO
3Be Xi Yuan, heating and decomposition obtains SnO
2Hollow ball shell.Be carbon source with glucose again, prepare carbon and coat SnO
2Hollow Sphere Composites is again through high-temperature process, with SnO
2Be reduced to Sn, finally obtain carbon and coat tin composite material, wherein the Sn grain diameter is about 100nm [Zhang, W.M.; Hu, J.S.; Guo, Y.G.; Zheng, S.F. Zhong, L.S.; Song, W.G.; Wan, L.J.Adv.Mater .2008,20,1160-1165].Another kind of thinking is, selects for use the carbon-coating of the reservation cavity that has prepared to do main body, is filled into the Sn nano particle in the carbon-coating again.At first prepare the NG+MWCNT main body as waiting, utilize the liquid impregnation method then, Sn
2+To immerse in the main body, and again through high-temperature process, finally obtain carbon and coat tin composite material, wherein the Sn grain diameter is 400-500nm.[Yi-Ruei?Jhan；Jenq-Gong?Duh；Su-Yueh.J.Diamond&Related?Materials，.2011，20，413-417]。So far, though people prepare tin/carbon composite, technology is too complicated; Inapplicable a large amount of preparation, and the tin particles size is bigger, has limited the further lifting of capacity of lithium ion battery; And raw material adopts organic tin salt, cost height, contaminated environment more.
Summary of the invention
To the existing problem of above-mentioned technology, the invention provides a kind of carbon-coated nano tin particles composite negative pole material, form as following weight percent: carbon 20%～80wt%, tin 20wt%～80wt%.
The further preferred version of the present invention is: tin particles is uniformly distributed in the three-dimensional grid carbon base body, and the tin particles diameter is 3～5nm
Another object of the present invention is to provide a kind of method for preparing carbon-coated nano tin particles composite negative pole material, make by following method:
Step 1: mass ratio was taken by weighing carbon source and Xi Yuan in 1: 5～1: 0.5; Take by weighing hexamethylenetetramine at 5: 1 according to Xi Yuan and hexamethylenetetramine mass ratio; Then carbon source, Xi Yuan and hexamethylenetetramine are distributed in the organic solvent; Be stirred to organic solvent under the room temperature and volatilize fully, obtain solid mixture;
Step 2: will go up step gained solid mixture and place retort, and in inert atmosphere, progressively be warming up to 400～900 ℃ of charings from normal temperature, insulation 2～5h promptly gets carbon-coated nano tin particles composite negative pole material.
The further preferred version of the present invention is: carbon source is selected from a kind of in phenolic resins, epoxy resin, the Lauxite.
The further preferred version of the present invention is: Xi Yuan is selected from a kind of in stannous chloride, stannous sulfate, the stannic chloride.
The further preferred version of the present invention is: organic solvent is selected from a kind of in pyridine, absolute ethyl alcohol, the ether.
The present invention confines tin particles owing to adopt the resinae carbon source to form three dimensional network structure; Thereby obtain composite material that nano level tin particles is uniformly distributed in carbon matrix as lithium ion battery negative material, the volumetric expansion problem that occurs in the time of effectively avoiding tin to do negative material.Make negative material have higher reversible capacity and good cyclical stability.Through electrochemical property test, reversible capacity is 0.2mA/cm up to 815mAh/g in current density first
2Circulate after 50 times, capacity can keep 362～446mAh/g.
Method provided by the invention only needs just can obtain tridimensional network carbon-coated nano tin composite material through mix, carbonization process, has characteristics such as technology is simple, the material preparation cost is low, free from environmental pollution, is prone to realize mass preparation.
Description of drawings
Accompanying drawing 1 carbon source is phenolic resins and the Xi Yuan transmission electron microscope picture when being stannous sulfate.
Accompanying drawing 2 carbon sources are phenolic resins and the Xi Yuan chemical property comparison diagram when being stannous sulfate.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated:
Embodiment 1:
Take by weighing 2g phenolic resins and 2g stannous chloride (SnCl at 1: 1 by mass ratio
22H
2O), press stannous chloride (SnCl
22H
2O) take by weighing the 0.4g hexamethylenetetramine at 5: 1 with the hexamethylenetetramine mass ratio.Then carbon source, Xi Yuan and hexamethylenetetramine are distributed in the 30ml absolute ethyl alcohol, are stirred to absolute ethyl alcohol under the room temperature and volatilize fully, obtain solid mixture.The gained solid mixture is put into retort, under the nitrogen atmosphere, be warming up to 600 ℃ from room temperature, be incubated 2 hours, take out after being cooled to room temperature, promptly get the carbon-coated nano tin composite material according to 1 ℃/min.Show that according to thermal weight loss (TG) analysis Sn content is 49wt%, the content of carbon is 51wt%.
Show that like accompanying drawing 1 transmission electron microscope (HRTEM) analysis tin particles is uniformly distributed in the carbon base body of three dimensional network structure, the tin particles diameter is 3～5nm.
2 electrochemical property test results show like accompanying drawing, this composite material 0.2mA/cm
2Still maintain 378mAh/g behind following 50 stable circulations of current density.
Embodiment 2
Take by weighing 2g phenolic resins and 10g stannous chloride (SnCl at 1: 5 by mass ratio
22H
2O), press stannous chloride (SnCl
22H
2O) take by weighing the 2g hexamethylenetetramine at 5: 1 with the hexamethylenetetramine mass ratio, add the 30ml pyridine and mix.Be stirred to absolute ethyl alcohol under the room temperature and volatilize fully, obtain solid mixture.The gained solid mixture is put into retort, under the nitrogen atmosphere, be warming up to 900 ℃ from room temperature, be incubated 1 hour, take out after being cooled to room temperature, promptly get the carbon-coated nano tin composite material according to 1 ℃/min.Show that according to thermal weight loss (TG) analysis Sn content is 74wt%, the content of carbon is 26wt%.
Electrochemical property test is the result show, this composite material material 0.2mA/cm
2Hold 362mAh/g behind following 50 stable circulations of current density.
Embodiment 3
Take by weighing 2g phenolic resins and 1g stannous chloride (SnCl at 1: 0.5 by mass ratio
22H
2O), press stannous chloride (SnCl
22H
2O) take by weighing the 0.2g hexamethylenetetramine at 5: 1 with the hexamethylenetetramine mass ratio, add the 30ml absolute ethyl alcohol and stirring and mix.Be stirred to absolute ethyl alcohol under the room temperature and volatilize fully, obtain solid mixture.The gained solid mixture is put into retort, under the nitrogen atmosphere, be warming up to 400 ℃ from room temperature, be incubated 5 hours, take out after being cooled to room temperature, promptly get the carbon-coated nano tin composite material according to 1 ℃/min.Show that according to thermal weight loss (TG) analysis Sn content is 32wt%, the content of carbon is 68wt%.
Electrochemical property test is the result show, this composite material material 0.2mA/cm
2Still maintain 365mAh/g behind following 50 stable circulations of current density.
Embodiment 4:
Take by weighing 2g phenolic resins and 2g stannous sulfate (SnSO at 1: 1 by mass ratio
42H
2O), press stannous sulfate (SnSO
42H
2O) take by weighing the 0.4g hexamethylenetetramine at 5: 1 with the hexamethylenetetramine mass ratio, add the 30ml ether and mix.Be stirred to ether under the room temperature and volatilize fully, obtain solid mixture.The gained solid mixture is put into retort, under the nitrogen atmosphere, be warming up to 600 ℃ from room temperature, be incubated 2 hours, take out after being cooled to room temperature, promptly get the carbon-coated nano tin composite material according to 1 ℃/min.Show that according to thermal weight loss (TG) analysis Sn content is 54wt%, the content of carbon is 46wt%.
The electrochemical property test result shows this composite material material 0.2mA/cm
2Hold 446mAh/g behind following 50 stable circulations of current density.
Below preferred embodiment of the present invention is specified; But the present invention is not limited to said embodiment; Those of ordinary skill in the art also can make all modification that is equal to or replacement under the prerequisite of spirit of the present invention, modification that these are equal to or replacement all are included in the application's claim institute restricted portion.
Claims (6)
1. a carbon-coated nano tin particles composite negative pole material is characterized in that: form as following weight percent: carbon 26%～68wt%, tin 32wt%～74wt%.
2. carbon-coated nano tin particles composite negative pole material according to claim 1, it is characterized in that: tin particles is uniformly distributed in the three-dimensional grid carbon base body, and the tin particles diameter is 3～5nm.
3. method for preparing the said carbon-coated nano tin particles of claim 1 composite negative pole material is characterized in that making by following method:
Step 1: mass ratio was taken by weighing carbon source and Xi Yuan in 1: 5～1: 0.5; Take by weighing hexamethylenetetramine at 5: 1 according to Xi Yuan and hexamethylenetetramine mass ratio; Then carbon source, Xi Yuan and hexamethylenetetramine are distributed in the organic solvent; Be stirred to organic solvent under the room temperature and volatilize fully, obtain solid mixture;
Step 2: will go up step gained solid mixture and place retort, and in inert atmosphere, progressively be warming up to 400～900 ℃ of charings from normal temperature, insulation 2～5h promptly gets carbon-coated nano tin particles composite negative pole material.
4. like the said method for preparing carbon-coated nano tin particles composite negative pole material of claim 2, it is characterized in that: said carbon source is selected from a kind of in phenolic resins, epoxy resin, the Lauxite.
5. like the said method for preparing carbon-coated nano tin particles composite negative pole material of claim 2, it is characterized in that: said Xi Yuan is selected from a kind of in stannous chloride, stannous sulfate, the stannic chloride.
6. like the said method for preparing carbon-coated nano tin particles composite negative pole material of claim 2, it is characterized in that: said organic solvent is selected from a kind of in pyridine, absolute ethyl alcohol, the ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101187986A CN102779984A (en) | 2011-05-09 | 2011-05-09 | Carbon-cladded nanometer tin particle composite negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101187986A CN102779984A (en) | 2011-05-09 | 2011-05-09 | Carbon-cladded nanometer tin particle composite negative electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102779984A true CN102779984A (en) | 2012-11-14 |
Family
ID=47124823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101187986A Pending CN102779984A (en) | 2011-05-09 | 2011-05-09 | Carbon-cladded nanometer tin particle composite negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102779984A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489860A (en) * | 2015-12-15 | 2016-04-13 | 昆明仁旺科技有限公司 | Anode material for lithium-ion battery and preparation method of anode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008210618A (en) * | 2007-02-26 | 2008-09-11 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| CN101494286A (en) * | 2007-12-04 | 2009-07-29 | 法拉赛斯能源公司 | Secondary battery material |
| CN101723315A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Preparation method of Sn/C nano composite material with nucleocapsid structure |
| CN101850959A (en) * | 2010-05-31 | 2010-10-06 | 奇瑞汽车股份有限公司 | Method for preparing silicon-carbon cathode material of lithium ion battery |
-
2011
- 2011-05-09 CN CN2011101187986A patent/CN102779984A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008210618A (en) * | 2007-02-26 | 2008-09-11 | Hitachi Maxell Ltd | Nonaqueous electrolyte secondary battery |
| CN101494286A (en) * | 2007-12-04 | 2009-07-29 | 法拉赛斯能源公司 | Secondary battery material |
| CN101723315A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Preparation method of Sn/C nano composite material with nucleocapsid structure |
| CN101850959A (en) * | 2010-05-31 | 2010-10-06 | 奇瑞汽车股份有限公司 | Method for preparing silicon-carbon cathode material of lithium ion battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489860A (en) * | 2015-12-15 | 2016-04-13 | 昆明仁旺科技有限公司 | Anode material for lithium-ion battery and preparation method of anode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106025221B (en) | A kind of preparation method of silicon/carbon graphite composite negative pole material | |
| CN107623116B (en) | Lithium ion battery cathode composite material and preparation method thereof | |
| CN105762329B (en) | A kind of silicon substrate composite negative pole material and preparation method for lithium ion battery | |
| CN103682272B (en) | A kind of lithium ion battery cathode material and its preparation method | |
| CN108923036A (en) | The preparation method of carbon-lithium composite powder and preparation method thereof, lithium metal electrode for secondary battery | |
| CN102376937A (en) | Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof | |
| CN104409703A (en) | Preparation method for molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material and application of molybdenum disulfide/nitrogen-doped graphene three-dimensional composite material | |
| CN105932284B (en) | A kind of close cladded type composite material and preparation method of mesoporous carbon and application | |
| CN109244427A (en) | Carbon coating zinc sulphide loads preparation method of the graphene as kalium ion battery cathode | |
| CN109461890A (en) | Silicon-carbon cathode material, preparation method and lithium ion battery | |
| CN109671929A (en) | The Li-Si alloy composite negative pole material and preparation method thereof of sulfide electrolyte cladding | |
| CN108899486A (en) | Sulfur electrolyte-coated positive electrode active material and preparation method thereof, and all-solid-state lithium sulfur battery and preparation method thereof | |
| CN102683649A (en) | Method for preparing lithium ion battery carbon silicon anode material | |
| CN107749461A (en) | A kind of preparation method of carbon coating silicon tin composite negative plate | |
| CN106848220B (en) | A kind of preparation method of graphene-iron oxide-graphene composite structure cell negative electrode material | |
| Zhang et al. | Constructing Biomass‐Based Ultrahigh‐Rate Performance SnOy@ C/SiOx Anode for LIBs via Disproportionation Effect | |
| CN105140464B (en) | Carbon bag nickel oxide nano piece is supported on nano composite material on Graphene and preparation method thereof | |
| CN108199014A (en) | A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications | |
| CN106784698A (en) | Si/SiC/C composites and preparation method and lithium ion battery negative and battery | |
| CN108878154A (en) | The preparation method of sodium titanate nano-fiber material and using the material as the sodium ion mixed capacitor of cathode | |
| CN110125429A (en) | A kind of preparation method and applications of sige alloy composite material | |
| CN108899550A (en) | Compound coating positive electrode active materials and preparation method thereof, anode material for lithium-ion batteries and solid lithium ion battery | |
| CN108666543A (en) | A kind of spongy C-SiC composite material and preparation methods in sea | |
| CN109786711A (en) | A kind of preparation method of porous carbon skeleton cladding tin combination electrode material | |
| CN104659346A (en) | Germanium/carbon composite negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121114 |