CN103219499B - A kind of preparation method of lithium ion battery silicon oxide/carbon composite negative pole material - Google Patents
A kind of preparation method of lithium ion battery silicon oxide/carbon composite negative pole material Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of lithium ion battery silicon oxide/carbon composite negative material, belong to new material and electrochemical field, problem to be solved is to provide a kind of lithium ion battery electrode material compared with height ratio capacity and good circulation stability and economically viable preparation technology.The present invention take tetraethoxysilane as silicon source, and nitric acid and ammoniacal liquor are pH value regulator, adopts citric acid auto-combustion method in conjunction with process of thermal treatment, prepares nano silicon oxide/carbon compound cathode materials.The invention has the advantages that powder granule is tiny and even, and there is porous character.The technical process of material is simple, and mild condition is consuming time few, is convenient to scale preparation.Silicon oxide/carbon composite negative material prepared by the method has comparatively height ratio capacity and good circulation stability, is a kind of desirable lithium ion battery negative material.
Description
Technical field
The invention belongs to new material and electrochemical field, be specifically related to a kind of novel can charging-discharging lithium ion battery silicon oxide/carbon composite negative material and preparation method thereof.
Technical background
The fast development of portable electric appts and electric vehicle, requires that lithium ion battery possesses the advantages such as high power capacity, high security, high-energy-density.But the actual lithium storage content of current commercial graphite negative material of lithium ion battery used more and more its theoretical capacity of convergence (graphite theoretical capacity is 372mAh/g, 855mAh/cm
3), seriously limit lithium ion battery and apply widely.For meeting the demand of high performance lithium ion battery to high-capacity cathode material, the lithium ion battery negative electrode material of Novel high-specific capacity flexible must be researched and developed.
Silicium cathode causes the extensive concern of researchers with the theoretical lithium storage content (4200mAh/g) of its superelevation.But silicon-based anode easily causes electrode to ftracture and efflorescence up to the change in volume of 300% in charge and discharge process, and then causes electrode capacity to be decayed rapidly; And the electron conduction ability of silicon is poor, affect the performance of active component capacity and the high rate performance of electrode.For the above shortcoming of silicon, researchers have passed a lot of methods to improve the chemical property of silica-base material.
Preparing silica based composites is wherein a kind of highly effective approach.Silica material can form nano Si particle and nonactive phase Li in embedding lithium process first
2o and Li
4siO
4, active phase Si even particulate dispersion, in nonactive phases, forms silicon based composite material.Nonactive phase can prevent the reunion of nano Si particle on the one hand, and all right effectively bulk effect of buffer Si in charge and discharge process, obtains good cycle performance simultaneously.Therefore be oxidized silica-based composite negative pole material to cause researchers and pay close attention to widely.
At present in this field, people generally adopt the methods such as high temperature evaporation to prepare commercial Nano-meter SiO_2 powder, and as silicon source, further modification is carried out to it, as it mixed with graphite or amorphous carbon material, preparing SiO/C composite negative pole material by high-energy ball milling.Si-SiO for silicon source, by high-energy ball milling and high-temperature heat treatment, prepares with commercialization silica powder in power supply research institute Liu Xing river, Tianjin seminar
2-C composite.With electrode prepared by this material, its first reversible capacity be 730mAh/g, the capability retention after 80 times that circulates is about 80%(Z.Lu, etal.JournalofPowerSources195 (2010): 4304-4307).Chil-HoonDoh seminar of electrician research institute of Korea S carries out high-energy ball milling process to commercialization silica powder and graphite mixing and prepares SiO/C composite material, with electrode prepared by this material, its first discharge specific capacity and charge specific capacity are respectively 1556 and 693mAh/g(C.H.Doh,, 30 circulation after reversible capacity still have 688mAh/g etal.JournalofPowerSources179 (2008): 367-370).Also some researchers are had to utilize hydro thermal method to prepare silica based composites.Inst. of Physics, CAS Wang Zhaoxiang teaches research group and utilizes TEOS for silicon source, prepares silicon dioxide/hard carbon composite negative pole material by hydro thermal method.With electrode prepared by this material, its first reversible specific capacity up to 630mAh/g(B.Guo, etal.ElectrochemistryCommunications10 (2008): 1876-1878), but cycle performance is general.This seminar take tetraethoxysilane as silicon source, silica/carbon composite is prepared in conjunction with heat treatment by st ber method, electrode cycle reversible capacity is about 800mAh/g, there is good cycle performance (J.Wang, etal.JournalofPowerSources196 (2011): 4811-4815).
Adopt business-like silica powder be raw material due to preparation method, cause its price costly, and preparation silica powder performance not easy-regulating.The technique such as high-energy ball milling and hydro thermal method simultaneously, the danger that productive rate is low, operation tool is certain, is unfavorable for the industrial applications being oxidized silicon based anode material.
Low-temperature combustion synthesis technology (LCS) is a kind of material synthesis technology of rising in recent years, and it adopts slaine saturated aqueous solution-organic-fuel mixture to be raw material, synthesizing superfine powder under lower firing temperature and combustion heat release temperature.The appearance of LCS is the important expansion to SHS technology (SHS), and the preparation for nano-powder opens new approach.Liquid phase batching ensure that the dispersed of each component, and firing temperature is lower by (200 ~ 500
oc), combustion process is rapid, and technique is simple, consumes energy low.This reaction liberated heat makes reaction spontaneously carry out, and synthetic product, has autocatalytic characteristics.And in course of reaction, discharge a large amount of gas, cause combustion product to expand into loose foam, avoid intergranular hard aggregation, be conducive to the dispersion of powder granule.Since the later stage nineties, adopt the research of LCS synthesis oxide nano-powder to receive researchers and more and more paid close attention to.Adopt LCS technology to prepare silica based composites, can obtain the nanoporous powder of good dispersion, this process yields is large, is convenient to scale preparation.
Summary of the invention
The object of the present invention is to provide that a kind of particle is tiny, even particle size distribution, there is the preparation method of the lithium ion battery silicon oxide/carbon composite negative pole material of good electrical chemical property, it is characterized in that: by combustion method of citric acid in conjunction with Post isothermal treatment, prepare nanoscale silicon/carbon composite.This preparation method is simple, cost is low, mild condition is consuming time few, and be convenient to scale preparation, the material of synthesis possesses good chemical property.
Its concrete steps are:
(1) solution is configured: select citric acid, take required quality, be dissolved in deionized water, stir to settled solution, in the solution of formation, citric acid concentration controls at 0.04 ~ 0.2mol/100ml, and this solution is designated as solution A;
Select tetraethoxysilane to be silicon source, measure volume required, be dissolved in a certain amount of absolute ethyl alcohol, stir formation clear solution.Wherein the volume ratio of absolute ethyl alcohol and tetraethoxysilane controls: absolute ethyl alcohol/tetraethoxysilane=1 ~ 5, and this solution is designated as solution B;
(2) under agitation, in solution A, drip red fuming nitric acid (RFNA), the addition of red fuming nitric acid (RFNA) controls at 5 ~ 20ml/100ml solvent, utilizes ammoniacal liquor to regulate the pH value of solution A 3 ~ 7 afterwards;
(3) solution B is added drop-wise to pH value in the solution A of 3 ~ 7, stir formation solution C;
(4) by solution C Keep agitation 3h, to move in porcelain unit ware and to be placed in baking oven and to carry out drying, oven temperature being raised carry out combustion reaction afterwards, obtain precursor product;
(5) precursor product of step (4) gained is heat-treated, obtain nano silicon oxide/carbon compound cathode materials powder.
Step (2) selects the ammoniacal liquor of weight percentage 25 ~ 28%, and percentage by weight be the nitric acid of 65% as pH value regulator, dropwise join in solution.
Solution B addition described in step (3), makes citric acid in solution C control with the ratio of the amount of substance of tetraethoxysilane: citric acid/tetraethoxysilane=1 ~ 4.
In baking oven described in step (4), drying is 70 ~ 100
odry 6 ~ 10h under C environment.
Combustion reaction temperature described in step (4) is 240 ~ 300
oc, temperature retention time is 2 ~ 4h.
Heat treatment described in step (5) is, under nitrogen or argon atmosphere, precursor product is warming up to 600 ~ 800
oc is incubated 1 ~ 4h, cools to room temperature with the furnace.
The present invention adopts combustion method of citric acid in conjunction with Post isothermal treatment, prepares nanoscale silicon/carbon composite.The invention has the advantages that preparation process is simple, reaction condition is gentle, and cost is low, consuming time few, is convenient to large-scale production; The silica prepared in this approach/carbon composite particle is tiny, and uniform particle sizes has good electrical chemical property, is a kind of desirable lithium ion battery negative material, can be widely used in the fields such as various portable electric appts, electric automobile and Aero-Space.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve chart of the silicon oxide/carbon composite negative material of embodiment 1.
Fig. 2 is the circulation volume figure of the silicon oxide/carbon composite negative material of embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to protection scope of the present invention:
Embodiment 1:
Take 9.4g citric acid, be dissolved in 90ml deionized water, stir to settled solution, be designated as solution A.Under agitation, in solution A, drip red fuming nitric acid (RFNA) 6.1ml, utilize ammoniacal liquor to regulate the pH value of solution A to be 6 afterwards; Measure 10ml tetraethoxysilane to be dissolved in 50ml absolute ethyl alcohol, stir to settled solution, be designated as solution B.Solution B being added drop-wise to pH value is in the solution A of 6, formed solution C, Keep agitation 3h, move into porcelain unit ware in and be placed in 80
ocarry out dry 8h in C baking oven, afterwards oven temperature is elevated to 250
oc, insulation 2h, obtains precursor product.Under nitrogen protection atmosphere, precursor product is warming up to 600
oc is incubated 1h, cools to room temperature with the furnace and obtains nano material powder.By obtained silica/carbon composite and acetylene black and PVdF in mass ratio for 70:15:15 mixes, making slurry, be evenly coated on Copper Foil, be stamped into circular electrode pole piece after vacuum drying, is to electrode with lithium metal, 1mol/LLiPF
6/ DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, composition test cell.Constant current charge-discharge test is carried out to battery, charging/discharging voltage scope is 0.01 ~ 2.5V, result shows, it has good chemical property, under the current density of 0.1A/g, first discharge specific capacity and charge specific capacity are respectively 1524.7 and 858.4mAh/g, and the specific capacity of material after 100 times that circulates is 509.5mAh/g.
Embodiment 2:
Take 9.4g citric acid, be dissolved in 90ml deionized water, stir to settled solution, be designated as solution A.Under agitation, in solution A, drip red fuming nitric acid (RFNA) 9.15ml, utilize ammoniacal liquor to regulate the pH value of solution A to be 5 afterwards; Measure 15ml tetraethoxysilane to be dissolved in 50ml absolute ethyl alcohol, stir to settled solution, be designated as solution B.Solution B being added drop-wise to pH value is in the solution A of 5, formed solution C, Keep agitation 3h, move into porcelain unit ware in and be placed in 80
ocarry out dry 8h in C baking oven, afterwards oven temperature is elevated to 250
oc, insulation 2h, obtains precursor product.Under nitrogen protection atmosphere, precursor product is warming up to 650
oc is incubated 1h, cools to room temperature with the furnace and obtains nano material powder.By obtained silica/carbon composite and acetylene black and PVdF in mass ratio for 70:15:15 mixes, making slurry, be evenly coated on Copper Foil, be stamped into circular electrode pole piece after vacuum drying, is to electrode with lithium metal, 1mol/LLiPF
6/ DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, composition test cell.Constant current charge-discharge test is carried out to battery, charging/discharging voltage scope is 0.01 ~ 2.5V, result shows, it has good chemical property, under the current density of 0.1A/g, first discharge specific capacity and charge specific capacity are respectively 1437.2 and 849.7mAh/g, and the specific capacity of material after 50 times that circulates is 493.6mAh/g.
Embodiment 3:
Take 9.4g citric acid, be dissolved in 90ml deionized water, stir to settled solution, be designated as solution A.Under agitation, in solution A, drip red fuming nitric acid (RFNA) 9.15ml, utilize ammoniacal liquor to regulate the pH value of solution A to be 6 afterwards; Measure 7ml tetraethoxysilane to be dissolved in 50ml absolute ethyl alcohol, stir to settled solution, be designated as solution B.Solution B being added drop-wise to pH value is in the solution A of 7, formed solution C, Keep agitation 3h, move into porcelain unit ware in and be placed in 80
ocarry out dry 8h in C baking oven, afterwards oven temperature is elevated to 280
oc, insulation 2h, obtains precursor product.Under nitrogen protection atmosphere, precursor product is warming up to 800
oc is incubated 1h, cools to room temperature with the furnace and obtains nano material powder.By obtained silica/carbon composite and acetylene black and PVdF in mass ratio for 70:15:15 mixes, making slurry, be evenly coated on Copper Foil, be stamped into circular electrode pole piece after vacuum drying, is to electrode with lithium metal, 1mol/LLiPF
6/ DMC+DEC+EC(volume ratio is 1:1:1) be electrolyte, Celgard2400 is barrier film, composition test cell.Carry out constant current charge-discharge test to battery, charging/discharging voltage scope is 0.01 ~ 2.5V, and result shows, it has good chemical property, and under the current density of 0.1A/g, first discharge specific capacity and charge specific capacity are respectively 1257.7 and 721.9mAh/g.
Claims (2)
1. a preparation method for lithium ion battery silicon oxide/carbon composite negative pole material, is characterized in that by combustion method of citric acid in conjunction with Post isothermal treatment, and prepare nanoscale silicon/carbon composite, concrete technology step is:
(1) solution is configured: the citric acid taking required quality, is dissolved in deionized water, stirs to settled solution, and in the solution of formation, citric acid concentration controls at 0.04-0.2mol/100ml, and this solution is designated as solution A;
Tetraethoxysilane is selected to be silicon source, measure volume required, be dissolved in a certain amount of absolute ethyl alcohol, stir formation clear solution, wherein the volume ratio of absolute ethyl alcohol and tetraethoxysilane controls: absolute ethyl alcohol/tetraethoxysilane=1-5, and this solution is designated as solution B;
(2) under agitation, in solution A, drip red fuming nitric acid (RFNA), the addition of red fuming nitric acid (RFNA) controls at 5-20ml/lOOml solvent, utilizes ammoniacal liquor to regulate the pH value of solution A at 3-7 afterwards;
(3) solution B is added drop-wise to pH value in the solution A of 3-7, stir formation solution C; Described solution B addition, makes citric acid in solution C control with the ratio of the amount of substance of tetraethoxysilane: citric acid/tetraethoxysilane=1-4;
(4) by solution C Keep agitation 3h, to move in porcelain unit ware and to be placed in baking oven and to carry out drying, oven temperature being raised carry out combustion reaction afterwards, obtain precursor product; In described baking oven, drying is dry 6-10h under 70-100 DEG C of environment, and described combustion reaction temperature is 240-300 DEG C, and temperature retention time is 2-4h;
(5) precursor product of step (4) gained is heat-treated, obtain nano silicon oxide/carbon compound cathode materials powder;
Heat treatment described in step (5) is under nitrogen or argon atmosphere, precursor product is warming up to 600-800 DEG C of insulation 1-4h, cools to room temperature with the furnace.
2. the preparation method of lithium ion battery silicon oxide/carbon composite negative pole material according to claim 1, it is characterized in that: step (2) selects weight percentage to be the ammoniacal liquor of 25-28%, and percentage by weight be the nitric acid of 65% as pH value regulator, dropwise join in solution.
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| CN106340630B (en) * | 2016-11-21 | 2018-10-09 | 安庆师范大学 | A kind of SiO2The preparation method of/C composite nano materials and its application in lithium cell cathode material |
| CN111029554A (en) * | 2019-12-25 | 2020-04-17 | 湖北万润新能源科技发展有限公司 | Preparation method and application of in-situ carbon-coated silicon dioxide-carbon composite material |
| CN111403744A (en) * | 2020-03-25 | 2020-07-10 | 广东凯金新能源科技股份有限公司 | Nitrogen-containing silicon oxygen carbon compound composite negative electrode material of lithium ion secondary battery and preparation method |
| CN113428866B (en) * | 2021-06-23 | 2023-03-31 | 宁夏大学 | Wool-line-ball-shaped SiOx/C and preparation method and application thereof |
| CN115893496B (en) * | 2022-11-10 | 2024-02-20 | 北京科技大学 | Composite anode material MnF2@C of lithium ion battery and preparation method thereof |
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| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
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| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
Non-Patent Citations (2)
| Title |
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| Facile preparation and electrochemical properties of amorphous SiO2/C composite as anode material for lithium ion batteries;Pengpeng Lv等;《Journal of Power Sources》;20130321;第237卷;第291-294页 * |
| 锂离子电池SiO／C复合负极材料的制备及性能研究;王静等;《实验技术与管理》;20120531;第29卷(第5期);第69-72页 * |
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