CN103258988B - A kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof - Google Patents

A kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof Download PDF

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CN103258988B
CN103258988B CN201310143447.XA CN201310143447A CN103258988B CN 103258988 B CN103258988 B CN 103258988B CN 201310143447 A CN201310143447 A CN 201310143447A CN 103258988 B CN103258988 B CN 103258988B
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sio
silicon
carbon
composite
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CN103258988A (en
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杨学林
石长川
王风军
周永涛
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CHINA SCIENCES HENGDA GRAPHITE Co Ltd
China Three Gorges University CTGU
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CHINA SCIENCES HENGDA GRAPHITE Co Ltd
China Three Gorges University CTGU
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Abstract

A kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite is be made up of the following component with parts by weight: silicon monoxide 5-7 part, carbohydrate 1-2 part, natural flake graphite 1-4 part.When preparing this composite negative pole material, carry out high-energy ball milling and high temperature pyrolysis by after mixing of materials, finally grind the composite material that sieves to obtain.This composite negative pole material, has excellent cycling performance and volumetric properties, for the practical of SiO negative material provides certain feasibility option; And its preparation method is simple to operate, environment friendly and pollution-free, be easy to promote.

Description

A kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof
Technical field
The invention belongs to field of electrochemical power source, be specifically related to a kind of lithium ion battery silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof.
Background technology
Lithium ion battery, since early 1990s research and development and success, has become the best battery system of current combination property with its superior performance advantages such as (as high in operating voltage) specific energy are high, good cycle, long service life, operating temperature range are wide, memory-less effect, self discharge are little, pollution-free.But along with portable type electronic product miniaturization and lithium ion battery, the demand in aviation, military affairs and automobile industry is day by day vigorous, and capacity and the energy density of battery urgently increase substantially.At present, commercial lithium-ion batteries mainly adopts the modified natural graphite and Delanium with excellent cycling performance as its negative material, but because of its theoretical specific capacity (LiC 6vs.372mAh/g) lower, therefore people place high hopes for Novel high-specific capacity flexible, long circulation life negative material.
Silicon monoxide (SiO) negative material gets more and more people's extensive concerning because having the cycle performance of high specific capacity (2400mAh/g) and excellence, is expected to the substitute products as silicon/carbon/graphite in lithium ion batteries material with carbon element.But using SiO as lithium ion battery negative material, its reversibility is unsatisfactory, and main cause is as follows: SiO can generate electrochemicaUy inert phase Li in embedding lithium process first 2o and Li 4siO 4(5SiO+6Li → Li 2o+Li 4siO 4+ 4Si); In follow-up embedding/de-lithium process, amorphous silicon is lithium-storing precursor (Si+xLi → Li xbut its intrinsic conductivity is low by (6.7 × 10 Si), -4s/cm) change in volume large (80 ~ 400%) and in embedding/de-process of lithium ion.The low meeting of conductivity makes charge transfer between active material particle be obstructed, and the stress that change in volume produces can cause that silicon grain breaks, efflorescence, finally can because the electrical contact between silicon grain and between particle and collector is lost and lose efficacy.For the problems referred to above, Recent study personnel are to SiO x(0≤x≤2) base negative material conducts in-depth research.On the one hand, SiO crystallite dimension dropped to sub-micron or nanoscale to subtract the change of short grained absolute volume by high-energy ball milling method, but when particle size is reduced to below 30nm, nano particle is easily reunited, in repeated charge process, easily " electrochemistry sintering " phenomenon occurs, cycle performance reduces on the contrary; On the other hand, by Nano-meter SiO_2 Granular composite in electrochemicaUy inert phase or electro-chemical activity phase matrix, absorb silicon grain change in volume by means of matrix phase and then stop granule atomization to lose efficacy.Wherein, what the most extensively adopt is utilize hydro-thermal charing, high temperature pyrolysis organic matter precursor (polyvinyl alcohol, poly furfuryl alcohol etc.), chemical vapour deposition (CVD) and sol-gal process etc. that SiO Granular composite is prepared SiO in amorphous carbon matrix x/ C composite negative pole material, utilize the advantages such as the little and good conductivity of amorphous carbon light weight, bulk effect effectively can improve the cycle performance of SiO negative material, but its long-term cyclical stability and volumetric properties still has much room for improvement.In addition, utilize the high temperature disproportionated reaction of SiO, method such as metal (Mg, Li etc.) thermal reduction, chemical etching etc. can prepare and have nucleocapsid, nest shape and loose structure Si/SiO xcomposite negative pole material, prepared composite material has excellent cycle performance and higher reversible capacity, but complicated, the high preparation cost of preparation technology, even need to use have severe corrosive, toxicity HF as etching liquid, thus hinder its practicalization.
Summary of the invention
The object of this invention is to provide a kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite and preparation method thereof, this composite negative pole material has excellent cycling performance and volumetric properties, and the simple environmental protection of preparation method, for the practical of SiO negative material provides certain feasibility option.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite, it is characterized in that: be made up of the following raw material with parts by weight: silicon monoxide 5-7 part, carbohydrate 1-3 part, natural flake graphite 1-4 part; Wherein, amorphous carbon is obtained after high temperature pyrolysis by used carbohydrate.
The composite negative pole material optimized is be made up of the following component with parts by weight: silicon monoxide 6 parts, 2 parts, carbohydrate, natural flake graphite 2 parts.
Fixed carbon content >=99% of described natural flake graphite.
Carbohydrate molecule formula meets C nh 2no m, and m≤n, often adopt glucose, sucrose, fructose etc.
A preparation method for high-performance silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite, concrete steps are:
1) proportionally take silicon monoxide, carbohydrate and natural flake graphite and be placed in ball grinder, high-energy ball milling 5h, rotational speed of ball-mill is 475rpm;
2) under an argon atmosphere, the material after ball milling is sintered 2h and 3h respectively at 200-250 DEG C and 900-1100 DEG C, after cool with stove;
3) cooled material grinds, crosses 300 mesh sieves in agate mortar, obtains silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite.
Described ball grinder is stainless steel jar mill, places with quality of material than the stainless steel steel ball for 20:1 in ball grinder.
Carry out in ar gas environment during described ball grinder sealing.
The advantages such as the little and good conductivity of amorphous carbon light weight, bulk effect effectively can improve the cycle performance of SiO negative material.
Composite negative pole material provided by the invention, compared with other pure SiO negative material, has following outstanding feature:
1) after mechanical ball milling and high temperature sintering process, Nano-meter SiO_2 particle is by amorphous carbon bonding and be scattered in equably on natural graphite scale, makes material have graphite good cycling stability and the high dual characteristics of silicon monoxide capacity concurrently.
2) carbohydrate is after Pintsch process, the amorphous carbon generated can not only the change in volume of buffer Si O, can also effectively act as " connecting media " of Nano-meter SiO_2 particle and crystalline flake graphite, effectively improve graphite linings and contact effect with SiO is intergranular, the electric charge that SiO particle can be made to accumulate in embedding/de-lithium process of electrochemistry can transmit fast by means of graphite linings, therefore, material has excellent volumetric properties and circulation performance.
3) building-up process is not with an organic solvent, and technique is simple, be easy to operation.
4) material preparation cost is low, and preparation method is simple to operate, environment friendly and pollution-free.
Accompanying drawing explanation
Below silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite is called SiO/C/G composite negative pole material, and the SiO/C/G composite material of different ratio is designated as xSi/yC/zG.
Fig. 1 is SiO raw material and prepared SiO/C/G(6Si/yC/zG) X-ray diffracting spectrum of composite material.
Fig. 2 is the stereoscan photograph of 6Si/2C/2G composite negative pole material under the enlargement ratio of 20000.
Fig. 3 is the stereoscan photograph of 6Si/2C/2G composite negative pole material under the enlargement ratio of 150000.
Fig. 4 is energy spectrogram (EDXmapping) of 6Si/2C/2G composite material in the corresponding region, A place of Fig. 2.
Fig. 5 is the comparison diagram of the cycle performance of SiO and different proportion SiO/C/G composite material.
The chemical property of Fig. 6 different proportion SiO/C/G composite material under different charge-discharge magnification.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing, comparative example, embodiment, but embodiment is only the present invention is described, instead of is limited.
For convenience of description, first comparative example is described, and then each embodiment is compared with it, demonstrated effect of the present invention.
Comparative example:
After SiO powder and acetylene black (DENKA, Japan) mixing, add in the deionized water solution containing sodium carboxymethylcellulose (CMC analyzes pure, traditional Chinese medicines) and blend together slurry; This liquid quality fraction is the mass ratio of 2.0%, SiO raw material, acetylene black and CMC is 3:1:1.The slurry obtained is coated on Copper Foil, through super-dry, rushes film and press mold makes work electrode.Be to electrode with metallic lithium foil, 2400 polypropylene screens are barrier film, 1MLiPF 6/ (EC+DMC) solution (LB-301, Zhangjiagang Cathay Huarong) is electrolyte, under the constant current of 0.15mA, carries out charge-discharge test in the voltage range of 0.02 ~ 1.5V.Embedding lithium capacity is 1550.1mAhg first -1, de-lithium capacity is 920.2mAhg -1, the embedding lithium capacity of 100 circulations is 534.5mAhg -1, de-lithium capacity is 532.5mAhg -1, its capability retention is 57.9%, and capacity attenuation is larger.In cyclic process, the conductivity of silicon is poor, and change in volume is comparatively large, thus causes its chemical property not good.
Embodiment 1:
Be 5:1:4 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, glucose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 5Si/1C/4G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 889.7mAhg -1, de-lithium capacity is 420.8mAhg -1; The embedding lithium capacity of 100 circulations is 637.1mAhg -1, de-lithium capacity is 635.7mAhg -1, its capability retention is 151.1%, and capacity has ascendant trend gradually, and its volumetric properties and cyclical stability comparatively SiO raw material improve significantly.
Embodiment 2:
Be 5:2:3 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, glucose and natural flake graphite, heat-treat after mechanical ball milling 5h under argon shield, ball-milling technology and the specific embodiments described in the equal summary of the invention of heat-treat condition.Then the 5Si/2C/3G composite material of gained is prepared electrode and carry out electro-chemical test, the assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1176.7mAhg -1, de-lithium capacity is 684.6mAhg -1, the embedding lithium capacity of 100 circulations is 724.6mAhg -1, de-lithium capacity is 722.9mAhg -1, its capability retention is 105.6%, and capacity is substantially undamped, and comparatively SiO raw material and 5Si/1C/4G composite material increase significantly.The increase of SiO content is conducive to the whole volume level improving composite material, and the content of graphite of 30% also ensure that its good conductivity, enables its capacity obtain stable release.
Embodiment 3:
Be 6:1:3 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, sucrose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 6Si/1C/3G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1156.8mAhg -1, de-lithium capacity is 628.6mAhg -1, the embedding lithium capacity of 100 circulations is 822.6mAhg -1, de-lithium capacity is 817.3mAhg -1, its capability retention is 130%, and capacity has ascendant trend gradually, and comparatively SiO raw material improves significantly.
Embodiment 4:
Be 6:2:2 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, sucrose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 6Si/2C/2G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1673.8mAhg -1, de-lithium capacity is 1068.7mAhg -1; The embedding lithium capacity of 100 circulations is 1113.4mAhg -1, de-lithium capacity is 1108.9mAhg -1, its capability retention is 103.8%, and capacity is without obvious attenuation trend, and comparatively SiO raw material and 6Si/1C/3G composite material all have further raising.The chemical property of its excellence mainly to Nano-meter SiO_2 because of ball milling refinement and high degree of dispersion, amorphous carbon matrix to the cushioning effect of Si change in volume and the improvement of graphite to conductivity of composite material relevant, as shown in Figure 2.
Embodiment 5:
Be 6:3:1 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, sucrose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 6Si/3C/1G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1638.8mAhg -1, de-lithium capacity is 964.7mAhg -1; The embedding lithium capacity of 100 circulations is 1012.1mAhg -1, de-lithium capacity is 1008.9mAhg -1its capability retention is 104.6%, and capacity is without obvious attenuation trend, but the comparatively 6Si/2C/2G composite material decrease to some degree of volumetric properties and cycle performance, this is main relevant with the reduction of content of graphite in composite material, but still has improvement to a great extent relative to SiO raw material.
Embodiment 6:
Be 7:1:2 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, fructose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 7Si/1C/2G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1324.9mAhg -1, de-lithium capacity is 734.7mAhg -1; The embedding lithium capacity of 100 circulations is 1050.7mAhg -1, de-lithium capacity is 1046.5mAhg -1its capability retention is 143.4%, capacity is in ascendant trend gradually, and this is mainly relevant with the cushioning effect of amorphous carbon to Si change in volume obtained after the electric conductivity of native graphite excellence in composite material and fructose high temperature pyrolysis, and comparatively SiO raw material improves significantly.
Embodiment 7:
Be 7:2:1 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, fructose and natural flake graphite, heat-treat under argon shield after mechanical ball milling 5h, ball-milling technology and heat-treat condition are all with reference to above-mentioned specific embodiment.The 7Si/2C/1G composite material of gained is prepared electrode and carries out electro-chemical test.The assembling of electrode preparation method battery and test condition are all with comparative example 1.
By test obtain material first embedding lithium capacity be 1681.8mAhg -1, de-lithium capacity is 1038.2mAhg -1; The embedding lithium capacity of 100 circulations is 787.8mAhg -1, de-lithium capacity is 787.2mAhg -1, its capability retention is 75.8%, and capacity is in attenuation trend gradually, and this is main relevant with the reduction of content of graphite in composite material, but still has improvement to a certain extent relative to SiO raw material.
Fig. 1 is SiO raw material and prepared SiO/C/G(6Si/yC/zG) X-ray diffracting spectrum of composite material.As can be seen from the figure, in composite material, there is obvious graphite diffraction maximum, describe native graphite after ball milling and still maintain good crystal structure.In addition, without the diffraction maximum of elemental silicon in the XRD collection of illustrative plates of composite material, illustrate that, under the pyrolysis temperature of 900 DEG C, SiO still exists with amorphous state.
Fig. 2 with Fig. 3 is the stereoscan photograph under the different enlargement ratio of 6Si/2C/2G composite negative pole material, and Fig. 4 is energy spectrogram (EDXmapping) of 6Si/2C/2G composite material in the corresponding region, A place of Fig. 2.As can be seen from Fig. 2 and Fig. 3, after mechanical ball milling and high temperature pyrolysis, Nano-meter SiO_2 particle is bondd by amorphous carbon and is dispersed on crystalline flake graphite, consistent with being uniformly distributed of Si, C, O element in its energy spectrogram.
Fig. 5 compared for the cycle performance of SiO and different proportion SiO/C/G composite material.Therefrom can find out, compared to SiO raw material, after coating modification, the chemical property of composite material is significantly improved.When SiO content one timing, the cyclical stability of composite material declines along with the reduction of content of graphite.Wherein, when silicon/carbon in composite material/graphite quality is than during for 6:2:2, composite material has best chemical property.Its first reversible specific capacity be 1068.7mAhg -1, after 100 circulations, its reversible capacity still can maintain 1108.9mAhg -1, capability retention is 103.8%.
Fig. 6 is the chemical property of different proportion SiO/C/G composite material under different charge-discharge magnification.Therefrom known, SiO raw material, 6Si/1C/3G, 6Si/2C/2G and 6Si/3C/1G composite material first reversible capacity are respectively 1373.2,676.6,1060.8 and 947.7mAhg -1.Wherein, the specific capacity of 6Si/2C/2G composite material under different multiplying and cyclical stability better than other material.At 0.15C(0.25mA/mg), under 0.3C and 2C multiplying power, its reversible capacity is about 1043.4,1003.9 and 816.6mAhg respectively -1, cyclical stability is better, substantially without capacity attenuation in 10 circulations; Under 4C multiplying power, its capacity is decayed to some extent, but still can maintain 560mAhg -1above, comparatively SiO raw material has clear improvement.

Claims (1)

1. a preparation method for silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite, is characterized in that, concrete steps are:
Be 6:2:2 by Si/C/G mass ratio, accurately take a certain amount of SiO powder, sucrose and natural flake graphite, the material after ball milling is sintered 2h and 3h respectively at 200-250 DEG C and 900-1100 DEG C after mechanical ball milling 5h under an argon atmosphere, after cool with stove; Cooled material grinds in agate mortar, cross 300 mesh sieves, obtains silicon monoxide/amorphous carbon/composite cathode material of silicon/carbon/graphite.
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