CN102403491A - Silicon carbon composite anode material of lithium-ion battery, method for preparing silicon carbon composite anode material, and lithium-ion battery - Google Patents
Silicon carbon composite anode material of lithium-ion battery, method for preparing silicon carbon composite anode material, and lithium-ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title abstract description 27
- 239000011870 silicon-carbon composite anode material Substances 0.000 title abstract 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010439 graphite Substances 0.000 claims abstract description 56
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 41
- 239000010406 cathode material Substances 0.000 claims description 23
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 21
- 235000013312 flour Nutrition 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 230000004087 circulation Effects 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 13
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000013081 microcrystal Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 29
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract 1
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- 150000001875 compounds Chemical class 0.000 description 6
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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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 provides a silicon carbon composite anode material of a lithium-ion battery, a method for preparing the silicon carbon composite anode material, and the lithium-ion battery. The silicon carbon composite anode material comprises two groups of substances, such as (a) silicon powder, silicon oxide (SiO) powder or a mixture of the silicon powder and the SiO powder, and (b) graphite and expanded graphite. The method for preparing the silicon carbon composite anode material comprises the following steps of: mixing components (a) and components (b); placing a mixture into a ball mill; and ball-milling for 1 to 24 h at the rotation speed of 100 to 600 r/min. By the method, the preparation process is simple and cost is low. The prepared anode material has excellent conducting performance. Correspondingly, the lithium-ion battery is high in specific capacity and good in cycle performance.
Description
Technical field
The invention belongs to battery manufacturing technology field, be specifically related to a kind of preparation method and battery of lithium ion battery negative material.
Background technology
Exhaustion day by day along with fossil fuel; And the fast development of portable electric appts and electric vehicle; The research of new forms of energy such as power-supply battery has become the focus that the whole world is paid close attention to, and wherein lithium ion battery is because of its energy density is high, power density is high, good cycle, environmental friendliness, structure variation and excellent specific property such as cheap are used widely.With regard to the structure of lithium ion battery, it mainly is made up of positive pole, negative pole, barrier film and electrolyte, and can the electrode performance of negative material further improve the decisive factor that becomes restriction lithium ion battery performance.
To the demand for development of lithium-ion-power cell, require objectively that negative material has that high power capacity, rapid rate discharge and recharge, characteristics such as high thermal stability and low cost.The more negative material of practical application is a material with carbon element at present; Like native graphite, graphitization carbonaceous mesophase spherules etc.; Wherein the theoretical capacity of graphite cathode material is 372mAh/g; Actual capacity is at 320-350mAh/g, and high-rate charge-discharge capability is poor, has limited the development of lithium ion battery aspect high power capacity and high power.In non-carbon negative pole material, the theoretical capacity of silicon the highest (lithium storage content of monocrystalline silicon is 3800mAh/g), lithium and silicon form alloy Li
xSi (0＜x≤4.4) is when forming Li
4.4Theoretical capacity during the Si compound is up to 4200mAh/g, much larger than the theoretical capacity of graphite; But the alloying of Si-Li alloy and removal alloying are accompanied by huge change in volume, and its volumetric expansion is up to 300%, the efflorescence render electrical electrode structure unstability of silicon and losing efficacy.Particularly common pure silicon, stable circulation is very poor, and the capacity that circulates after 5 times is just almost nil from reducing to more than the 3000mAh/g.
At present; More effectively prepare carbon-silicon composite material in the method for modifying to the proposition of lithium ion battery negative material the problems referred to above and alleviate the volumetric expansion in the battery charge and discharge process, the method has been widely used in the study on the modification of lithium ion battery negative material.
Address this problem two kinds of methods are arranged usually: the one, deposition obtains silicon thin film on collector; The advantage of this method is need not add other component in the electrode; Shortcoming is that this preparation process is not suitable for large-scale production; And after the thickness of silicon fiml surpassed 1 micron, the diffusion length of lithium ion increased, the corresponding increase of resistance and stress.The 2nd, preparation activity-inertia compound system material is alleviated the volumetric expansion in the charge and discharge process, like carbon-silicon composite material.
Preparing activity-inertia compound system material is the method for utilizing " buffering skeleton " to come compensative material to expand.In theory, as long as the electrode potential of two kinds of materials is incomplete same, the phase of electro-chemical activity just can be embedded in the active skeleton of relative non-electrochemical, and non-active material plays the effect that disperses and cushion medium.Utilize the coordinating effect between each component of composite material, can reach the purpose of mutual supplement with each other's advantages, the method has been widely used in the study on the modification of lithium ion battery negative material.
Carbonaceous negative material change in volume in charge and discharge process is less relatively, and is the good conductor of electronics, therefore is selected as the dispersible carrier of dispersed silicon particle.The chemical property of silicon and carbon is close in addition, can combine closely.Silicon grain is if can be nano-dispersed in material with carbon element, the space between structure that material with carbon element itself is had and the silicon grain that is nano-dispersed all can be lithium ion provides a large amount of passages, increases the embedded location of lithium ion.Compound can the reaching of carbon silicon improved the silicon bulk effect, improves the purpose of its electrochemical stability.Therefore multiple material with carbon element is used to the negative material with compound preparation high power capacity of silicon and excellent cycle performance.
One Chinese patent application numbers 200510030785.8 discloses the patent that name is called " a kind of lithium ion battery silicon/carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof "; This method is with silica flour and graphite mixing and ball milling; Dry after adding carbohydrate solutions again; And add concentrated sulfuric acid dehydration carbonization, obtain the composite negative pole material that silicon, graphite and amorphous carbon are formed after the washing drying.This method technology is simple, carries out carburizing reagent at normal temperatures and has reduced energy consumption, but use volatile concentrated sulfuric acid in the preparation process, and to the environment deleterious impact, and graphite can not effectively suppress the silicon volumetric expansion, and prepared negative material cyclicity is bad.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art; A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof is provided; Technology is simple; Prepared silicon-carbon composite cathode material can effectively suppress the expansion of silicon volume, big, the good cycle of corresponding lithium ion battery specific capacity.
Solving the technical scheme that technical problem of the present invention adopted is that this silicon-carbon composite cathode material of lithium ion battery comprises following two groups of materials:
(a) mixture of silica flour or SiO powder or silica flour and SiO powder
(b) graphite and expanded graphite.
Expanded graphite is through intercalation processing, washing, drying, the expanded a kind of loose porous vermiform material that makes of heating by native graphite.Expanded graphite and graphite are hexagonal crystal system; So it had both kept advantageous properties such as thermal endurance, corrosion resistance, radiation resistance, electrical and thermal conductivity, self lubricity and the coefficient of friction of native graphite be low, also have performances such as resilience that native graphite do not have, adsorptivity.Expanded graphite is used for lithium ion battery negative material can reduce production costs; Improve the conductivity of electrode material; And owing to also have elasticity and compressibility under the expanded graphite normal temperature; The variation that can offset silicon volume in the charge and discharge process is kept original structure and is not destroyed, and effectively suppresses the bulk effect of silicon, has prolonged the cycle life of negative material.Expanded graphite also has adsorptivity in addition, and has loose porous structure, and the fine particle that ball milling produces can be filled in the expanded graphite pore space structure.
Simple expanded graphite specific area is very little, and tap density is low, be unfavorable for material processing (as the coating etc.), but add a part of graphite head it off.
Preferably, expanded graphite mass content is 5-95wt% in said (b), and (b) and (a) mass ratio is 10: 1-1: 4.
Further preferably, expanded graphite mass content is 40-70wt% in said (b), (a) is the mixture of silica flour and SiO powder, and (b) and (a) mass ratio is 4: 1-1: 1.Reach optimum performance, must contain a certain amount of silica flour in the said composite negative pole material.The about 1000mAh/g of SiO theoretical capacity, and the theoretical lithium storage content of silicon is 3800mAh/g.But all silica flour (a), then because the conference of silicon bulk effect causes prepared lithium ion battery cycle performance poor.
Preferably, graphite is one of Delanium, native graphite, micro crystal graphite or carbonaceous mesophase spherules in said (b).
Preferably, the particle diameter of silica flour is 0.05-5 μ m in said (a), and the SiO powder directly is 0.05-75 μ m.
Preferably, this composite negative pole material first discharge specific capacity remains on 364-601.2mAh/g at 714-1500.4mAh/g after 100 circulations.
The preparation method of above-mentioned silicon-carbon composite cathode material of lithium ion battery is: comprise above-mentioned (a) component mixed to be placed on (b) component and carry out ball milling in the ball mill.Diameter of particle is little behind the ball milling, contains silicon components and carbonaceous component and mixes more even, prepared negative material good cycle.
Further preferably, said component is mixed and is placed in the ball mill ball milling 1-24h under the 100-600r/min rotating speed.
The present invention also provides the lithium ion battery of above-mentioned composite negative pole material preparation, promptly comprises the negative pole according to the prepared battery of lithium ion battery silicon-carbon cathode material of the above preparation method's preparation.
The invention has the beneficial effects as follows: use simple and easy method to prepare silicon-carbon composite cathode material of lithium ion battery; Graphite and expanded graphite high thermal stability and low cost characteristics combine with the characteristics of silicon materials high power capacity; And improved the bulk effect of silicon, improved its electrochemical stability.Have marked improvement aspect the specific capacity of improving lithium ion battery and the cycle performance, by the battery of made of the present invention, first discharge specific capacity reaches 714-1500.4mAh/g, remains on 364-601.2mAh/g after 100 circulations.
Description of drawings
Fig. 1 is lithium ion battery silicon-carbon cathode material capacity cycle performance resolution chart in specific embodiment of the present invention.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing.
The embodiment of the invention provides a kind of silicon-carbon composite cathode material of lithium ion battery with height ratio capacity and excellent cycle performance.
Balls grinding machine of the present invention is the QM-3SP04 type planetary ball mill that Nanjing Univ. Instrument Factory produces.
Embodiment one
Take by weighing 1g silica flour, 1.2g graphite and 0.8g expanded graphite, mix the back and add in the ball mill, ball milling 12h under the rotating speed of 400r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
The negative material of gained is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF (Kynoar) at 80: 10: 10; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil; Drying is 24 hours under 80 ℃ of vacuum degree 0.02MP conditions, makes Experimental cell and uses pole piece.With the lithium sheet is to electrode, and electrolyte is 1mol/L LiPF
6EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Through test, the battery first discharge specific capacity of present embodiment made reaches 1500.4mAh/g, still remains on 601.2mAh/g after 100 circulations.Cycle performance figure is as shown in Figure 1.First discharge specific capacity is up to 1500.4mAh/g; Specific discharge capacity just drops to about 600mAh/g for the second time, and this is that violent volumetric expansion has taken place the silicon in the material because in the first charge-discharge process; Cause structure that destruction has been taken place to a certain extent, capacity attenuation is very obvious for the first time.But the prepared negative material of present embodiment is different from the negative material of single silicon components again, has effectively suppressed the bulk effect of silicon after compound with expanded graphite, and cycle performance of battery significantly improves, and still remains on about 600mAh/g until 100 circulations.
Embodiment two
Take by weighing 1g SiO powder, 1.2g graphite and 0.8g expanded graphite, mix the back and add in the ball mill, ball milling 8h under the rotating speed of 500r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 923mAh/g, still remains on 393mAh/g after 100 circulations.
Embodiment three
Take by weighing 0.5g silica flour, 0.5g SiO powder, 1.2g graphite and 0.8g expanded graphite, mix the back and add in the ball mill, ball milling 20h under the rotating speed of 300r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1123mAh/g, still remains on 550mAh/g after 100 circulations.
Embodiment four
Take by weighing 0.5g silica flour, 0.5g SiO powder, 1g graphite and 1g expanded graphite, mix the back and add in the ball mill, ball milling 4h under the rotating speed of 450r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1214mAh/g, still remains on 556mAh/g after 100 circulations.
Embodiment five
Take by weighing 0.5g silica flour, 0.5g SiO powder, 0.6g graphite and 1.4g expanded graphite, mix the back and add in the ball mill, ball milling 24h under the rotating speed of 220r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1183mAh/g, still remains on 574mAh/g after 100 circulations.
Embodiment six
Take by weighing 0.25g silica flour, 0.25g SiO powder, 1g graphite and 1g expanded graphite, mix the back and add in the ball mill, ball milling 8h under the rotating speed of 400r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 714mAh/g, still remains on 364mAh/g after 100 circulations.
Embodiment seven
Take by weighing 1g silica flour, 1g SiO powder, 1g graphite and 1g expanded graphite, mix the back and add in the ball mill, ball milling 12h under the rotating speed of 350r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1044mAh/g, still remains on 634mAh/g after 100 circulations.
Embodiment eight
Take by weighing 0.5g silica flour, 0.5g SiO powder, 0.1g graphite and 1.9g expanded graphite, mix the back and add in the ball mill, ball milling 24h under the rotating speed of 220r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1203mAh/g, still remains on 568mAh/g after 100 circulations.
Embodiment nine
Take by weighing 0.5g silica flour, 0.5g SiO powder, 1.9g graphite and 0.1g expanded graphite, mix the back and add in the ball mill, ball milling 24h under the rotating speed of 220r/min obtains the product silicon-carbon composite cathode material of lithium ion battery.
Adopt embodiment one said method to prepare lithium ion battery, through testing: first discharge specific capacity reaches 1198mAh/g, still remains on 374mAh/g after 100 circulations.
By above detailed description, can understand that the battery specific capacity that the bulk effect that the invention solves conventional Si-C composite material complex process and can not effectively suppress silicon causes preparing is little, the problem of cycle performance difference to the embodiment of the invention.And first discharge specific capacity remains on 364-601.2mAh/g at 714-1500.4mAh/g after 100 circulations, is higher than the performance of silicon-based anode material prepared in the prior art.
It is understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (9)
1. silicon-carbon composite cathode material of lithium ion battery is characterized in that this composite negative pole material comprises following two groups of materials:
(a) mixture of silica flour or SiO powder or silica flour and SiO powder
(b) graphite and expanded graphite.
2. composite negative pole material according to claim 1 is characterized in that: the expanded graphite mass content is 5-95wt% in said (b) group, and (b) and (a) mass ratio is 10: 1-1: 4.
3. composite negative pole material according to claim 2 is characterized in that: expanded graphite mass content is 40-70wt% in said (b), (a) is the mixture of silica flour and SiO powder, and (b) and (a) mass ratio is 4: 1-1: 1.
4. according to the arbitrary described composite negative pole material of claim 1-3, it is characterized in that: graphite is one of Delanium, native graphite, micro crystal graphite or carbonaceous mesophase spherules in said (b).
5. according to the arbitrary described composite negative pole material of claim 1-3, it is characterized in that: the particle diameter of silica flour is 0.05-5 μ m in said (a), and the SiO powder directly is 0.05-75 μ m.
6. according to the arbitrary described composite negative pole material of claim 1-3, it is characterized in that this composite negative pole material first discharge specific capacity, remain on 364-601.2mAh/g after 100 circulations at 714-1500.4mAh/g.
7. the preparation method of a silicon-carbon composite cathode material of lithium ion battery is characterized in that comprising arbitrary said (a) component among the claim 1-5 and (b) component mixed to be placed on and carries out ball milling in the ball mill.
8. preparation method according to claim 7 is characterized in that component is mixed to be placed in the ball mill ball milling 1-24h under the 100-600r/min rotating speed.
9. a lithium ion battery is characterized in that comprising that the lithium ion battery silicon-carbon cathode material according to the said preparation method's preparation of claim 6 prepares the negative pole of battery.
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Cited By (33)
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| CN102832376A (en) * | 2012-08-13 | 2012-12-19 | 华南理工大学 | Preparation method for silicon carbon composite material for lithium ion battery negative electrode |
| CN102891293A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing anode composite material of lithium ion battery |
| CN103022453A (en) * | 2013-01-10 | 2013-04-03 | 上海中聚佳华电池科技有限公司 | Lithium ion battery negative electrode material Si@SiOx/graphene composite and preparation method thereof |
| CN103022448A (en) * | 2012-12-19 | 2013-04-03 | 天津巴莫科技股份有限公司 | Method for preparing lithium battery silicon carbon anode material |
| CN103219504A (en) * | 2013-03-28 | 2013-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof |
| CN103779536A (en) * | 2013-11-06 | 2014-05-07 | 南京安普瑞斯有限公司 | Silicon-containing negative electrode of lithium ion battery and preparation method of silicon-containing negative electrode |
| TWI514654B (en) * | 2013-04-12 | 2015-12-21 | 國家中山科學研究院 | Negative electrode material for lithium ion rechargeable battery and manufacturing method thereof |
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