CN102709565A - Preparation method of lithium ion battery porous silicon carbon composite negative material - Google Patents
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Abstract
The invention puts forwards a preparation method of a lithium ion battery porous silicon carbon composite negative material. The prepared porous silicon carbon composite material simultaneously has the characteristics of high capacity and excellent circulating stability. Micron silicon and nanometer aluminum powder are promoted to be compounded by utilizing a high-energy ball milling method, a porous silicon material can be formed through acid etching, and through a porous structure, the volume change of silicon in the discharging process is relieved to a great extent. Meanwhile, the stress generated by the volume change of the silicon can be effectively buffered through taking graphite as a dispersion matrix and in combination with a secondary surface amorphous carbon coating technology of the composite material, so that the circulating stability of the material is improved. The preparation method of the material has the advantages of simplicity, low cost and easiness in industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, be specifically related to a kind of preparation method of silicon-carbon composite cathode material of lithium ion battery.
Technical background
Lithium ion battery has been widely used in the portable equipments such as mobile portable phone, notebook as the chemical power source of green high-capacity environment-protecting.As the high-energy power power supply of high power batteries such as development electric automobile, motorcycle, be badly in need of improving the energy density of ion battery.At present the graphitic carbon class has better cycle performance as ion secondary battery cathode material lithium, but that shortcoming is a specific capacity is low, and the performance of carbon electrode receives preparation technology's influence bigger, has limited the industrialization of high energy lithium ion cells such as electrokinetic cell.Therefore, must seek the better negative material of performance.
In the R&D process of novel negative material, wherein silicon materials have the sight that very high theoretical embedding lithium capacity (4200 mAh/g) has attracted more and more researchers with it.Yet; The silicon-based anode material in charge and discharge process with bigger change in volume (＞300%); The change in volume that continues causes material structure avalanche and electrode material to peel off easily, and generation silicon grain breaks and powder phenomenon-tion, causes separating between conductive network and the silicon particle; Capacity descends fast, the cycle performance variation.To these problems; The method that researchers extensively adopt compoundization to prepare silicon based composite material improves its cycle performance; Utilize the cooperative effect between each component of composite material; Can reach the purpose of mutual supplement with each other's advantages, as carrying out compoundly all having obtained improvement to a certain degree with conducting polymer, metal nitride, Si oxide, but unsatisfactory.Having report to adopt nano-silicon is active material; And carrying out the amorphous carbon coating, the Si-C composite material of processing can possess high lithium storage content and excellent cycle performance simultaneously, like employing self assembly routes from bottom to top such as Magasinski; Prepared Si-C composite material with hierarchy; The porousness that particle itself has can be adjusted in and embed/deviate from the stereomutation of silicon in the process, reversible capacity reach 1950 mAh/g (Nature materials. 2010,9:353-358); Yet the nano-silicon expensive raw material price, yield poorly the very difficult realization industrialization with high costs of the Si-C composite material of preparation, commercial target.Kim etc. are raw material with cheap micron silica flour; Adopt mechanical force-chemical Prepared by Ball Milling and possessed Si-C composite material (the Journal of Power Sources. 2010 that reversible capacity reaches 613 mAh/g; 195:6031 – 6036); Li Hong etc. are that raw material has been invented a kind of Si-C composite material with " Lantern Festival " structure and had higher charging capacity and good fail safe (Granted publication CN 1328805C) with commercialization micron silicon, yet micron silicon active material yardstick is bigger, can have serious bulk effect in the charge and discharge process; Can lower the capacitance conservation rate in the cyclic process, the material cycle performance of preparation is relatively poor.
Summary of the invention
To above technical deficiency, the purpose of this invention is to provide a kind of preparation method of lithium ion battery cellular silicon-carbon composite cathode material, make the product that makes have both height ratio capacity and the good advantage of cycle performance simultaneously.
For realizing above-mentioned technical purpose, the present invention adopts following technical scheme:
A, silica flour and nanometer aluminium powder are by a certain percentage with 300 ~ 500 r/min rotating speed ball mill mixing, 6 ~ 12 h;
B, the composite material that makes in the steps A is immersed into concentration is in 2.0 ~ 3.0 mol/L hydrochloric acid; The relatively complete consumption that reactive aluminum is fallen of hydrochloric acid is added into 20% ~ 30%; In agitated reactor, stir 1.5 ~ 2 h; Filter the back with washed with de-ionized water to pH more than or equal to 5, in 90 ℃ ~ 110 ℃ oven dry down, make the cellular silicon materials;
C, the agraphitic carbon precursor that will coat usefulness are used dissolution with solvents; Cellular silicon materials and meso-position radius that adding step B makes are the spherical graphite of 6 ~ 14 μ m; The protection lower seal of inert gas in planetary or bearing-type ball grinder with 400 ~ 600 r/min rotating speeds or in the oscillatory type ball mill with vibration frequency ball milling 10 ~ 16 h of 5 ~ 20Hz, obtain mixed slurry;
D, under 90 ~ 110 ℃ of conditions, mixed slurry is carried out drying, cool to room temperature obtains cellular Si-C composite material precursor;
E, the precursor among the step D is put into the carbide furnace of inert gas shielding, rise to 850 ~ 1150 ℃ with 5 ~ 8 ℃/min heating rate, carbonization treatment 3 ~ 8 h are cooled to room temperature and make the cellular silicon-carbon composite cathode material after crushed.
F, repeat C, D, E operating procedure once, wherein the agraphitic carbon precursor adds at twice, and it is 1: 2 ~ 1: 0.6 that front and back add mass ratio.
Said silica flour account for the raw material gross mass 5% ~ 12%, graphite is 48% ~ 55%, all the other are the agraphitic carbon precursor.
The meso-position radius of said nanometer aluminium powder is 30 ~ 60 nm, and the meso-position radius of said silica flour is 1 ~ 3 μ m, and its ball milling mass ratio is 1: 3 ~ 1: 1.5.
Activated silica surface in the described silicon-carbon composite cathode material is a loose structure, and the surface distributed aperture is 10 ~ 80 nm, and meso-position radius is 0.5 ~ 1.0 μ m, and particle surface pore-size distribution number is 3.0 * 10
10~ 1.2 * 10
11/ cm
2
Said high energy ball mill is one or more of planetary ball mill, vibrator, bearing ball grinding machine.
Said agraphitic carbon precursor be pitch, citric acid, PVA, sucrose one or more.
Said solvent is that volume ratio is one or more of mixed solution, absolute ethyl alcohol, deionized water of 1: 1 oxolane and acetone.
Its meso-position radius of described silicon-carbon composite cathode material is 16 ~ 24 μ m, and tap density is 0.95 ~ 1.20 g/cm
3, specific area is 1.0 ~ 2.5 m
2/ g.
The silicon raw material that preparation method of the present invention uses is 1 ~ 3 μ m as the commercialization silica flour of cheapness, meso-position radius, and is with low cost, is easy to realize industrialization.Preparation method of the present invention carries out high-energy ball milling to nanometer aluminium powder and silica flour; The combination at enhancing body interface; Make solid-state atom diffuse to form compound; Remove the porous that aluminium matter can realize silicon materials through acid etch, the loose structure of preparation material can suppress the change in volume of silicon in the charge and discharge process well, improves the stability of material.Preparation method of the present invention disperses parent; The material of preparation can cushion the change in volume of silicon, and help silicon and in carbon, evenly disperse, thus the cyclical stability of raising composite material; And reduce the irreversible capacity first of composite material to a certain extent, improve first charge-discharge efficiency.Preparation method of the present invention takes into account the surperficial agraphitic carbon coating technology of composite material simultaneously; The material of preparation has the RESEARCH OF PYROCARBON of coating structure; Not only graphite and silica flour are carried out tight bond; And for silicon provides a continuous space network, can effectively cushion the stress of the change in volume generation of silicon, keep the stable of electrode material.
Embodiment
Below with the formal specification of embodiment and Comparative Examples product provided by the present invention and preparation method's substantive distinguishing features and conspicuousness progress; Embodiment is product of the present invention and the representative concrete scheme of preparation method, and product of the present invention and preparation method only are confined to embodiment.
Embodiment 1
With meso-position radius is the nanometer aluminium powder of 60 nm and the quality proportioning that commodity silica flour (meso-position radius is 3 μ m) is pressed 1: 3, in the high pure nitrogen atmosphere, is sealed in the ball grinder, places on the oscillatory type ball milling appearance, and rotational speed of ball-mill 300 r/min ball millings 12 h are set.The compound that ball milling is made is immersed in the hydrochloric acid of 2.0 mol/L; The relatively complete consumption that reactive aluminum is fallen of hydrochloric acid is added to stir 1.5 h into 30%; The filtration back is dried down more than or equal to 5,110 ℃ to pH with washed with de-ionized water and is made the cellular silicon materials, and recording the aperture is 10 ~ 60 nm; Meso-position radius is 0.9 μ m, and particle surface pore-size distribution number is 8.0 * 10
10/ cm
2It is until dissolving fully in 1: 1 the mixed solution of oxolane and acetone that 4.5 kg pitches are joined volume ratio.In the high pure nitrogen atmosphere, the artificial spherical graphite of 16.5 kg (meso-position radius is 14 μ m), 1.5 kg cellular silicon materials and carbon source solution are sealed in the ball grinder; With 400 r/min rotating speed ball millings, 16 h; With being placed in the carbide furnace that is connected with high pure nitrogen after the slurry oven dry that makes; Rise to 850 ℃ with 5 ℃/min heating rate, carbonization treatment 8 h are cooled to room temperature and obtain cellular Si-C composite material precursor.Composite material is joined in the solution that is dissolved with 7.5 kg pitches, behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon and coat, composite material is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its meso-position radius is 24 μ m, and tap density is 0.95 g/cm
3, specific area is 2.0 m
2/ g.
Compound, acetylene black, PVDF were processed electrode slice according to 80: 10: 10, were to electrode with metal lithium sheet, 1.0 mol/L LiPF
6/ EC: DMC (volume ratio 1: 1) is an electrolyte, is assembled into CR2430 type button cell, at 0.2 mA/cm
2Current density, 0.01 ~ 1.5 V discharges and recharges and carries out the charge-discharge performance test under the cut-ff voltage condition, and the result is as shown in table 1.
Embodiment 2
With meso-position radius is the nanometer aluminium powder of 30 nm and the quality proportioning that commodity silica flour (meso-position radius is 2 μ m) is pressed 1: 2; In argon atmosphere, be sealed in the ball grinder; Like embodiment 1 said preparation method with rotating speed 500 r/min ball milling 8 h on the planetary type ball-milling appearance; Add through the relatively complete consumption that reactive aluminum is fallen of 2.5 mol/L to filter behind 25% salt acid etch 2 h, with washed with de-ionized water to pH more than or equal to 5,100 ℃ of oven dry preparation cellular silicon materials down; Recording the aperture is 10 ~ 50 nm, and particle surface pore-size distribution number is 1.1 * 10
11/ cm
2, aperture number is 6000 on every meso-position radius particle.2.4 kg cellular silicon materials, 15.6 kg natural spherical plumbagos (meso-position radius is 6 μ m) and 5.0 kg are dissolved in the citric acid of absolute ethyl alcohol, in argon atmosphere, are sealed in the oscillatory type ball grinder, with vibration frequency ball milling 12 h of 15Hz.With being placed in the carbide furnace that is connected with argon gas after the slurry oven dry that makes, rise to 900 ℃ with 8 ℃/min heating rate, carbonization treatment 6 h.The cellular Si-C composite material precursor that makes joined behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon in the solution that is dissolved with 7.0 kg citric acids and coat, the composite material that makes is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its meso-position radius is 16 μ m, and tap density is 1.02 g/cm
3, specific area is 2.3 m
2/ g.
Electrode preparation, battery assembling and charge-discharge performance test are of embodiment 1, and test result is as shown in table 1.
Embodiment 3
With meso-position radius is the nanometer aluminium powder of 30 nm and the quality proportioning that commodity silica flour (meso-position radius is 2 μ m) is pressed 1: 2.5; In argon atmosphere, be sealed in the ball grinder;, add through the consumption that 3.0 mol/L fall reactive aluminum fully to filter behind 20% salt acid etch 2 h with rotating speed 350 r/min ball milling 10 h on bearing-type ball milling appearance like embodiment 1 said preparation method, with washed with de-ionized water to pH more than or equal to 5; Dry preparation cellular silicon materials down for 100 ℃; The aperture is 20 ~ 70 nm, and meso-position radius is 0.8 μ m, and particle surface pore-size distribution number is 5.0 * 10
10/ cm
23.0 kg cellular silicon materials, 15 kg natural spherical plumbagos (meso-position radius is 12 μ m) and 4.0 kg are dissolved in the PVA of deionized water, in argon atmosphere, are sealed in the ball grinder, with rotating speed 600 r/min ball millings 10 h.With being placed in the carbide furnace that is connected with argon gas behind the slurry vacuum drying that makes, rise to 1000 ℃ with 8 ℃/min heating rate, carbonization treatment 5 h.The cellular Si-C composite material precursor that makes joined behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon in the solution that is dissolved with 8.0 kgPVA and coat, composite material is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its meso-position radius is 20 μ m, and tap density is 1.10 g/cm
3, specific area is 1.4 m
2/ g.
Electrode preparation, battery assembling and charge-discharge performance test are of embodiment 1, and test result is as shown in table 1.
Embodiment 4
With meso-position radius is the nanometer aluminium powder of 60 nm and the quality proportioning that commodity silica flour (meso-position radius is 1 μ m) is pressed 1: 1.5; In the high pure nitrogen atmosphere, be sealed in the ball grinder;, add through the consumption that 3.0 mol/L fall reactive aluminum fully to filter behind 20% salt acid etch 1.8 h with rotating speed 400 r/min ball milling 8 h on the planetary type ball-milling appearance like embodiment 1 said preparation method, with washed with de-ionized water to pH more than or equal to 5; Dry preparation cellular silicon materials down for 90 ℃; The aperture is 20 ~ 80 nm, and meso-position radius is 0.6 μ m, and particle surface pore-size distribution number is 3.0 * 10
10/ cm
23.6 kg cellular silicon materials, the artificial spherical graphite of 14.4 kg (meso-position radius is 14 μ m) and 6.0 kg are dissolved in the sucrose of deionized water, in the high pure nitrogen atmosphere, are sealed in the ball grinder, with rotating speed 600 r/min ball millings 10 h.With being placed in the carbide furnace that is connected with high pure nitrogen behind the slurry vacuum drying that makes, rise to 1150 ℃ of preset temperatures with 7 ℃/min heating rate, carbonization treatment 3 h.The cellular Si-C composite material precursor that makes joined behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon in the solution that is dissolved with 6.0 kg sucrose and coat, composite material is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its meso-position radius is 23 μ m, and tap density is 1.20 g/cm
3, specific area is 1.0 m
2/ g.
Electrode preparation, battery assembling and charge-discharge performance test are of embodiment 1, and test result is as shown in table 1.
Embodiment 5
With meso-position radius is the nanometer aluminium powder of 30 nm and the quality proportioning that commodity silica flour (meso-position radius is 2 μ m) is pressed 1: 2.0; In argon atmosphere, be sealed in the ball grinder;, add to filter behind 30% salt acid etch, 2 h with rotating speed 500 r/min ball milling 12 h on the planetary type ball-milling appearance like embodiment 1 said preparation method through the consumption that 2.0 mol/L fall reactive aluminum fully, with washed with de-ionized water to pH more than or equal to 5; Dry preparation cellular silicon materials down for 110 ℃; The aperture is 10 ~ 40 nm, and meso-position radius is 0.5 μ m, and particle surface pore-size distribution number is 1.2 * 10
11/ cm
21.6 kg cellular silicon materials, 10.4 kg natural spherical plumbagos (meso-position radius is 6 μ m) and 3.4 kg are dissolved in the pitch of mixed solution that volume ratio is 1: 1 oxolane and acetone; In argon atmosphere, be sealed in the ball grinder, with rotating speed 500 r/min ball millings 12 h.With being placed in the carbide furnace that is connected with argon gas behind the slurry vacuum drying that makes, rise to 900 ℃ of preset temperatures with 8 ℃/min heating rate, carbonization treatment 6 h.The cellular Si-C composite material precursor that makes joined behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon in the solution that is dissolved with 4.6 kg pitches and coat, composite material is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its meso-position radius is 17 μ m, and tap density is 1.00 g/cm
3, specific area is 2.5 m
2/ g.
Electrode preparation, battery assembling and charge-discharge performance test are of embodiment 1, and test result is as shown in table 1.
Comparative Examples
It is 1: 1 the oxolane and mixed solution, 1.6 kg nano-silicons (meso-position radius is 50 nm) and 10.4 kg natural spherical plumbagos (meso-position radius is 12 μ m) the planetary type ball-milling jar of in being full of the glove box of argon gas, packing into of acetone that 3.4 kg pitches are dissolved in volume ratio, seals with O type circle.12 h are uniformly dispersed silicon and graphite with 500 r/min rotating speed ball millings; It is in 110 ℃ the drying box solvent to be volatilized fully that the uniform sizing material that obtains is transferred to temperature; Dried mixture moves in the crucible, and crucible is placed carbide furnace, feeds argon shield; Speed with 8 ℃/min is warmed up to 900 ℃, behind 900 ℃ of insulation 6 h, is cooled to room temperature.The composite material that makes joined behind ball milling-high temperature pyrolysis, carry out the secondary agraphitic carbon in the solution that is dissolved with 4.6 kg pitches and coat, composite material is pulverized with pulverizer, cross 325 mesh sieves repeatedly and obtain product.Recording its tap density is 0.94 g/cm
3, specific area is 1.0 m
2/ g.
Particle diameter be 13 ~ 15 μ m nano-silicone wire/carbon composite materials through being assembled into CR2430 type button cell like embodiment 1 described battery assemble flow, its charge-discharge performance is tested.
The electric performance test result of each embodiment and Comparative Examples is as shown in table 1
Table 1: the silicon-carbon composite cathode material electrical property that various embodiments of the present invention and Comparative Examples make
| Embodiment and Comparative Examples | Raw material consumption (Si: graphite: carbon source) | Specific capacity (mAh/g) first | Efficient (%) first | 300 circulation volume conservation rates (%) |
| Embodiment 1 (pitch) | 1.5: 16.5: 12 (4.5+7.5) | 502 | 82% | 83% |
| Embodiment 2 (citric acid) | 2.4: 15.6: 12 (5.0+7.0) | 590 | 85% | 87% |
| Embodiment 3 (PVA) | 3.0: 15.0: 12 (4.0+8.0) | 654 | 79% | 80% |
| Embodiment 4 (sucrose) | 3.6: 14.4: 12 (6.0+6.0) | 751 | 77% | 74% |
| Embodiment 5 (pitch) | 1.6: 10.4: 8.0 (3.4+4.6) | 608 | 87% | 90% |
| Comparative Examples (pitch) | 1.6: 10.4: 8.0 (3.4+4.6) | 621 | 75% | 65% |
Detect data from above-mentioned test and can find out that the cellular silicon-carbon cathode composite material that the inventive method makes not only possesses higher lithium storage content, shows good cycle performance simultaneously.The inventive method is simple, and is with low cost, is easy to industrialization.
Claims (8)
1. the preparation method of a lithium ion battery cellular silicon-carbon composite cathode material; It is characterized in that: the body interface that utilizes high-energy ball milling method to strengthen silica flour and nanometer aluminium powder combines; Form alloy material, prepare the cellular silicon materials through acid etch, to carry out ball milling compound with graphite microparticles again; Finally after carbon coats, make the cellular silicon-carbon composite cathode material, said method comprising the steps of:
A, silica flour and nanometer aluminium powder are by a certain percentage with 300 ~ 500 r/min rotating speed ball mill mixing, 6 ~ 12 h;
B, the composite material that makes in the steps A is immersed into concentration is in 2.0 ~ 3.0 mol/L hydrochloric acid; The relatively complete consumption that reactive aluminum is fallen of hydrochloric acid is added into 20% ~ 30%; In agitated reactor, stir 1.5 ~ 2 h; Filter the back with washed with de-ionized water to pH more than or equal to 5, in 90 ℃ ~ 110 ℃ oven dry down, make the cellular silicon materials;
C, the agraphitic carbon precursor that will coat usefulness are used dissolution with solvents; Cellular silicon materials and meso-position radius that adding step B makes are the spherical graphite of 6 ~ 14 μ m; The protection lower seal of inert gas in planetary or bearing-type ball grinder with 400 ~ 600 r/min rotating speeds or in the oscillatory type ball mill with vibration frequency ball milling 10 ~ 16 h of 5 ~ 20Hz, obtain mixed slurry;
D, under 90 ~ 110 ℃ of conditions, mixed slurry is carried out drying, cool to room temperature obtains cellular Si-C composite material precursor;
E, the precursor among the step D is put into the carbide furnace of inert gas shielding, rise to 850 ~ 1150 ℃ with 5 ~ 8 ℃/min heating rate, carbonization treatment 3 ~ 8 h are cooled to room temperature and make the cellular silicon-carbon composite cathode material after crushed;
F, repeat C, D, E operating procedure once, wherein the agraphitic carbon precursor adds at twice, and it is 1: 2 ~ 1: 0.6 that front and back add mass ratio.
2. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1 is characterized in that: said silica flour account for the raw material gross mass 5% ~ 12%, graphite is 48% ~ 55%, all the other are the agraphitic carbon precursor.
3. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1; It is characterized in that: the meso-position radius of said nanometer aluminium powder is 30 ~ 60 nm; The meso-position radius of said silica flour is 1 ~ 3 μ m, and its ball milling mass ratio is 1: 3 ~ 1: 1.5.
4. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1; It is characterized in that: the activated silica surface in the described silicon-carbon composite cathode material is loose structure; The surface distributed aperture is 10 ~ 80 nm; Meso-position radius is 0.5 ~ 1.0 μ m, and particle surface pore-size distribution number is 3.0 * 10
10~ 1.2 * 10
11/ cm
2
5. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1 is characterized in that: said high energy ball mill is one or more of planetary ball mill, vibrator, bearing ball grinding machine.
6. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1 is characterized in that: said agraphitic carbon precursor be pitch, citric acid, PVA, sucrose one or more.
7. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1 is characterized in that: said solvent is that volume ratio is one or more of mixed solution, absolute ethyl alcohol, deionized water of 1: 1 oxolane and acetone.
8. the preparation method of a kind of lithium ion battery cellular silicon-carbon composite cathode material according to claim 1 is characterized in that: its meso-position radius of described silicon-carbon composite cathode material is 16 ~ 24 μ m, and tap density is 0.95 ~ 1.20 g/cm
3, specific area is 1.0 ~ 2.5 m
2/ g.
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