CN101826612B - Preparation method of lithium ion battery silicon-carbon cathode material - Google Patents
Preparation method of lithium ion battery silicon-carbon cathode material Download PDFInfo
- Publication number
- CN101826612B CN101826612B CN2009100376663A CN200910037666A CN101826612B CN 101826612 B CN101826612 B CN 101826612B CN 2009100376663 A CN2009100376663 A CN 2009100376663A CN 200910037666 A CN200910037666 A CN 200910037666A CN 101826612 B CN101826612 B CN 101826612B
- Authority
- CN
- China
- Prior art keywords
- pitch
- cathode material
- preparation
- volume ratio
- carbon cathode
- 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)
Abstract
The invention relates to a preparation method of a lithium ion battery silicon-carbon cathode material, which comprises the following steps: 1.fully dispersing nanometer silicon powder into an asphalt solution; 2. mixing the asphalt solution obtained in step 1, furfural, a catalyst and a cosolvent, then pouring into a reaction flask, sealing, heating at the temperature of 50 to 100 DEG C, curing to obtain organic gel, and forming a coating of the nanometer silicon powder; and 3. drying a material obtained in step 2, and then carrying out carbonizing treatment in an inert atmosphere to prepare a product. The invention provides the preparation method of the lithium ion battery silicon-carbon cathode material which enables activated silica to exert higher capacity and simultaneously has good cycle performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material preparation method, be specifically related to the preparation method of Si-C composite material.
Technical background
The trend of electronic apparatus miniaturization, energetic, portability, the development and the exploitation of the development of space technology and the demand of defence equipment and electric automobile have higher requirement to the performance of lithium ion battery.And the improvement of lithium ion battery performance depends primarily on the raising of embedding lithium electrode material energy density and cycle life; The theoretical lithium storage content of the extensive graphite-like carbon negative pole material that adopts of lithium ion battery is lower at present; The demand that obviously can not adapt to development, so development of new high-performance negative material has become the task of top priority.
The Si sill more and more attracts attention because having the highest theoretical embedding lithium capacity (4200mAh/g is far above present other all negative material).But there is serious bulk effect in the Si sill under high level removal lithium embedded condition, causes the cyclical stability of electrode to descend significantly.How improving silicon materials is a present research emphasis as the cycle performance of lithium ion battery negative material.To the volume efficiency of silicon, silicon is compound with the carrier with elasticity and stable performance, the change in volume of buffering silicon; Though will be that to improve the charging and discharging capacity of effective way material with carbon element of silicon class stability of material lower, be difficult to satisfy the requirement of electric motor car and hybrid electric vehicle to cell high-capacityization, carbon class material has the structure of relative resilient; Be good lithium ion and electronic conductor; Itself have certain embedding lithium capacity, its doff lithium change in volume is little, good cycling stability.Therefore through the mutual supplement with each other's advantages between Si, C, be prepared into the excellent Si-C composite material of composite performance and have certain practical significance.The preparation Si-C composite material method of report has at present: vapour deposition, mechanical high-energy ball milling method, high temperature solid state reaction, sol-gel process etc.The vapour deposition process technical process is difficult to control, is difficult to obtain the product of uniformity, is unfavorable for commercially producing; The utilization of machinery high-energy ball milling method energy is lower, and length consuming time be unfavorable for energy-conservation and mass preparation, and cycle performance is relatively poor.The high temperature solid state reaction technical process is simple, but cyclical stability still remains to be improved.Cyclical stability, the electrochemical reversibility of sol-gel process gained material are all undesirable at present.
Summary of the invention:
To the deficiency of above technology, the object of the present invention is to provide a kind of rate of decay that can effectively prolong silicon-carbon cathode material, improve the lithium ion battery silicon-carbon cathode material preparation method of silicon-carbon cathode material cycle performance.
For realizing above-mentioned technical purpose, the present invention adopts following technical scheme:
A kind of preparation method of lithium ion battery silicon-carbon cathode material may further comprise the steps:
(1) pitch is dissolved in forms cold primer-oil in the toluene;
(2) in the cold primer-oil of step (1), add nano silica fume and fully dispersion;
(3) pour in the reaction bulb and sealing after the petroleum asphalt that step (2) is prepared according to predetermined formulation and furfural, catalyst and cosolvent mix, between 50～100 ℃, heat and obtained the organic solvent gel in 1～10 day;
(4) the organic solvent gel of (3) gained was placed the air air dry 2～10 days or about 1 day of first air dry then directly heating, drying obtained organic aerogel in 1～24 hour;
(5) organic aerogel with (4) gained places carbide furnace, heating carbonization under inert gas shielding, and 700～1300 ℃ of carburizing temperatures, carbonization time 60～180 minutes, product is taken out in cooling cooling naturally afterwards, obtains silicon carbon material.
The particle diameter of said nano silica fume is 30～50nm.
Said catalyst is sulfuric acid or hydrochloric acid.
Among the said preparation method, used each material mixture ratio is in step (1)～(3): the mass ratio of nano-silicon and pitch is 0.08-0.23; The mass volume ratio of pitch and furfural is 0.33-1g/ml; The mass volume ratio of pitch and catalyst is 0.5-20g/ml; Cold primer-oil and cosolvent volume ratio are 0.67-4; The mass volume ratio of pitch and total solvent is 0.05-0.25g/ml.
Said cosolvent is an acetate.
Little, the even particle size distribution of its granularity of employed nano-silicon in the inventive method can be alleviated the bulk effect of silicon to a certain extent.And the charcoal gel three-dimensional stacked porous material that forms that is a kind of nano particle has good electric conductivity simultaneously.The present invention utilizes pitch reactivity shortcut and simple to prepare the characteristic of organic aerogel and charcoal gel; The charcoal gel that with pitch is feedstock production coats; Because its internal structure can be cut out in the nano-scale range inner control, helps the nano-dispersed of nano silica fume, has so not only alleviated the bulk effect of silicon; And prolonged the rate of decay of silicon carbon material, improved the cycle performance of silicon carbon material.The inventive method preparation technology is simple, quick, equipment requirements is low.
Embodiment
Embodiment 1: according to following ratio: the mass ratio of nano-silicon and pitch is 0.15; The mass volume ratio of pitch and furfural is 0.5g/ml; The mass volume ratio of pitch and catalyst is 5g/ml; Asphalt solution and cosolvent volume ratio are 1; The mass volume ratio of pitch and total solvent is 0.1g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 70 ℃ to obtain organogel in 5 days; 1 day direct then heating, drying 5 hours (110 ℃) of air dry in air obtains organic aerogel then; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 900 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 180 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 2: according to following ratio: the mass ratio of nano-silicon and pitch is 0.08; The mass volume ratio of pitch and furfural is 1g/ml; The mass volume ratio of pitch and catalyst is 5g/ml; Asphalt solution and cosolvent volume ratio are 1; The mass volume ratio of pitch and total solvent is 0.05g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 90 ℃ to obtain organogel in 1 day; 1 day direct then heating, drying 7 hours (110 ℃) of air dry in air obtains organic aerogel then; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 700 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 180 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 3: according to following ratio: the mass ratio of nano-silicon and pitch is 0.23; The mass volume ratio of pitch and furfural is 0.33g/ml; The mass volume ratio of pitch and catalyst is 10g/ml; Asphalt solution and cosolvent volume ratio are 1; The mass volume ratio of pitch and total solvent is 0.1g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 50 ℃ to obtain organogel in 7 days; 1 day direct then heating, drying 15 hours (110 ℃) of air dry in air obtains organic aerogel then; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 1300 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 60 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 4: according to following ratio: the mass ratio of nano-silicon and pitch is 0.15; The mass volume ratio of pitch and furfural is 0.5g/ml; The mass volume ratio of pitch and catalyst is 20g/ml; Asphalt solution and cosolvent volume ratio are 0.67; The mass volume ratio of pitch and total solvent is 0.1g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 100 ℃ to obtain organogel in 2 days; 1 day direct then heating, drying 1 hour (120 ℃) of air dry in air obtains organic aerogel then; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 900 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 180 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 5: according to following ratio: the mass ratio of nano-silicon and pitch is 0.18; The mass volume ratio of pitch and furfural is 0.5g/ml; The mass volume ratio of pitch and catalyst is 5g/ml; Asphalt solution and cosolvent volume ratio are 1.44; The mass volume ratio of pitch and total solvent is 0.25g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 70 ℃ to obtain organogel in 7 days; Air dry 4 days in air then obtains organic aerogel; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 900 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 180 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 6: according to following ratio: the mass ratio of nano-silicon and pitch is 0.15; The mass volume ratio of pitch and furfural is 0.5g/ml; The mass volume ratio of pitch and catalyst is 0.5g/ml; Asphalt solution and cosolvent volume ratio are 4; The mass volume ratio of pitch and total solvent is 0.1g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 70 ℃ to obtain organogel in 7 days; Air dry 2 days in air then obtains organic aerogel; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 1100 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 120 minutes, cooling cooling naturally obtains silicon carbon material.
Embodiment 7: according to following ratio: the mass ratio of nano-silicon and pitch is 0.15; The mass volume ratio of pitch and furfural is 0.5g/ml; The mass volume ratio of pitch and catalyst (for hydrochloric acid) is 5g/ml; Asphalt solution and cosolvent volume ratio are 1; The mass volume ratio of pitch and total solvent is 0.1g/ml, adds in the reaction bulb each component and solvent and sealing, reacts down in 70 ℃ to obtain organogel in 10 days; 1 day direct then heating, drying 5 hours (110 ℃) of air dry in air obtains organic aerogel then; Afterwards, organic aerogel is placed desk-top retort, under the protection of high pure nitrogen, be warming up to 1300 ℃ with the rate of heat addition of 5 ℃/min from room temperature, constant temperature carbonization 60 minutes, cooling cooling naturally obtains silicon carbon material.
Above-mentioned each material property of implementing to make is detected:
With the above-mentioned silicon carbon material grind into powder that makes, cross 200 mesh sieves, be prepared into the electrode of lithium ion battery then, the lithium sheet is to electrode, the organic electrolyte that uses is 1M LiPF
6EC/DMC (1: 1, Vol), UBE3025 (PP/PE/PP) is a barrier film, makes button cell, test charging and discharging currents density is 0.2mA/cm
2, be 0～1.5V by charging/discharging voltage.
Record each embodiment data such as following table 1
Table 1, various embodiments of the present invention make the chemical property of material
Claims (5)
1. the preparation method of a lithium ion battery silicon-carbon cathode material may further comprise the steps:
A, pitch is dissolved in forms cold primer-oil in the toluene;
B, adding nano silica fume and fully dispersion in the cold primer-oil of step a;
Pour in the reaction bulb and sealing after c, the petroleum asphalt that step b is prepared according to predetermined formulation and furfural, catalyst and cosolvent mix, between 50～100 ℃, heat and obtained the organic solvent gel in 1～10 day;
D, with the organic solvent gel of c gained placed the air air dry 2～10 days or about 1 day of first air dry then directly heating, drying obtained organic aerogel in 1～24 hour;
E, the organic aerogel of d gained is placed carbide furnace, heating carbonization under inert gas shielding, carburizing temperature is 700～1300 ℃, carbonization time is 60～180 minutes, cooling cooling naturally afterwards, the taking-up product obtains Si-C composite material.
2. a kind of lithium battery silicon-carbon cathode material preparation method according to claim 1, the particle diameter that it is characterized in that said nano silica fume is 30～50nm.
3. a kind of lithium battery silicon-carbon cathode material preparation method according to claim 1 is characterized in that described catalyst is sulfuric acid or hydrochloric acid.
4. a kind of lithium battery silicon-carbon cathode material preparation method according to claim 1, it is characterized in that among the said preparation method that used each material mixture ratio is among step a～c: the mass ratio of nano-silicon and pitch is 0.08-0.23; The mass volume ratio of pitch and furfural is 0.33-1g/ml; The mass volume ratio of pitch and catalyst is 0.5-20g/ml; Cold primer-oil and cosolvent volume ratio are 0.67-4; The mass volume ratio of pitch and total solvent is 0.05-0.25g/ml.
5. a kind of lithium battery silicon-carbon cathode material preparation method according to claim 1 is characterized in that said cosolvent is an acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100376663A CN101826612B (en) | 2009-03-06 | 2009-03-06 | Preparation method of lithium ion battery silicon-carbon cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100376663A CN101826612B (en) | 2009-03-06 | 2009-03-06 | Preparation method of lithium ion battery silicon-carbon cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101826612A CN101826612A (en) | 2010-09-08 |
| CN101826612B true CN101826612B (en) | 2012-05-23 |
Family
ID=42690404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100376663A Expired - Fee Related CN101826612B (en) | 2009-03-06 | 2009-03-06 | Preparation method of lithium ion battery silicon-carbon cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101826612B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299306B (en) * | 2011-07-15 | 2015-01-21 | 中国科学院广州能源研究所 | Nano-silicon composite lithium ion battery cathode material with poly (3,4-ethylenedioxythiophene) as coating and carbon source and preparation method thereof |
| CN102306757B (en) * | 2011-08-26 | 2014-07-02 | 上海交通大学 | Silicon graphene composite anode material of lithium ion battery and preparation method of silicon graphene composite anode material |
| CN104993112A (en) * | 2015-06-23 | 2015-10-21 | 西安博纳材料科技有限公司 | Preparation method for silicon-carbon composite material |
| CN108183198B (en) * | 2016-12-08 | 2020-04-10 | 中国科学院大连化学物理研究所 | Lithium ion battery cathode material and preparation and application thereof |
| CN109962214B (en) * | 2017-12-14 | 2022-03-08 | 中国科学院大连化学物理研究所 | Carbon nano-layer coated silicon negative electrode material and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402366A (en) * | 2002-06-21 | 2003-03-12 | 中国科学院上海微系统与信息技术研究所 | High specific capacity Si-C composite material for cathode of Li ion cell, and mfg. method 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 |
-
2009
- 2009-03-06 CN CN2009100376663A patent/CN101826612B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1402366A (en) * | 2002-06-21 | 2003-03-12 | 中国科学院上海微系统与信息技术研究所 | High specific capacity Si-C composite material for cathode of Li ion cell, and mfg. method 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101826612A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101887966B (en) | Preparation method of composite hard carbon cathode material of lithium ion battery | |
| CN1199300C (en) | High specific capacity Si-C composite material for cathode of Li ion cell, and mfg. method thereof | |
| CN1913200B (en) | Silicon carbone compound negative polar material of lithium ion battery and its preparation method | |
| US9663860B2 (en) | Silicon-carbon composite anode material for lithium ion batteries and a preparation method thereof | |
| CN103311522B (en) | A kind of silicon/carbon composite microsphere negative electrode material and its production and use | |
| CN103078090B (en) | Lithium ion power battery composite cathode material and its preparation method | |
| CN103165862B (en) | A kind of high performance lithium ionic cell cathode material and preparation method thereof | |
| CN1909268B (en) | Lithium ion battery negative electrode material containing PC dissolvent electrolytic solution and its preparation method | |
| CN100338802C (en) | Cathode material of lithium ion cell and preparation method thereof | |
| CN102082272A (en) | Hard carbon coated lithium ion battery anode material and preparation method thereof | |
| KR20130030769A (en) | Composite hard carbon material of negative electrode for lithium ion battery and method for preparing the same | |
| CN111146416B (en) | Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery | |
| CN103094528A (en) | Hard carbon cathode material for lithium ion power and energy storage battery and preparation method of hard carbon cathode material | |
| CN104103821B (en) | The preparation method of silicon-carbon cathode material | |
| CN102227020B (en) | Preparation method of modified graphite cathode material for lithium ion battery | |
| CN102231434A (en) | Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof | |
| CN101632913B (en) | Preparation method of silicon/porous carbon nano-composite particle | |
| CN103560233A (en) | Carbon coated silicon graphite cathode material of lithium ion battery and preparation method thereof | |
| CN101924209A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN102694156A (en) | Silicon-carbon composite negative pole material, preparation method thereof and lithium ion battery using foamed metal as negative pole current collector | |
| CN102709563B (en) | Lithium ion battery silicon cathode material and preparation method thereof | |
| CN101826612B (en) | Preparation method of lithium ion battery silicon-carbon cathode material | |
| CN102881869A (en) | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material | |
| CN1242502C (en) | Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method | |
| CN102569752A (en) | Carbon modified material for lithium ion secondary battery cathode and preparation method for carbon modified material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Zeng Xianhua Document name: Notification of Passing Preliminary Examination of the Application for Invention |
|
| 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20150306 |
|
| EXPY | Termination of patent right or utility model |