CN101533907B - A kind of preparation method of lithium-ion battery silicon-based negative electrode composite material - Google Patents
A kind of preparation method of lithium-ion battery silicon-based negative electrode composite material Download PDFInfo
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- CN101533907B CN101533907B CN2009100821252A CN200910082125A CN101533907B CN 101533907 B CN101533907 B CN 101533907B CN 2009100821252 A CN2009100821252 A CN 2009100821252A CN 200910082125 A CN200910082125 A CN 200910082125A CN 101533907 B CN101533907 B CN 101533907B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 21
- 239000010703 silicon Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000000463 material Substances 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 238000007580 dry-mixing Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical group [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- 229910052786 argon Inorganic materials 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract 2
- 239000002994 raw material Substances 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 27
- 239000000395 magnesium oxide Substances 0.000 description 15
- 239000010405 anode material Substances 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- 238000007600 charging Methods 0.000 description 13
- 238000007599 discharging Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin 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
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Abstract
一种锂离子电池硅基负极复合材料的制备方法，属锂离子电池领域。将硅的氧化物和Mg粉进行称量配比，镁粉与硅的氧化物的加入量按照Mg/O原子比例0.1∶1～1.3∶1计算，并混合均匀，置于流动的氮气或氩气等惰性气氛中，以1～30℃/min的升温速率达到所需温度500～1000℃，保温0.5～6小时。然后程序控温冷却或断电自然冷却至室温。或将硅的氧化物、Mg和球进行称量配比，并将混合物放到球磨罐中，在惰性气氛下进行高能球磨，球料比1∶1～50∶1，转速100～3000转，球磨时间0.5～100小时。本发明的优点在于：原料成本低、工艺过程简单、耗时较少、产率高，而且产物具有良好的容量和循环性能。
The invention discloses a preparation method of a silicon-based negative electrode composite material for lithium ion batteries, belonging to the field of lithium ion batteries. The silicon oxide and Mg powder are weighed and proportioned. The amount of magnesium powder and silicon oxide added is calculated according to the Mg/O atomic ratio of 0.1:1 to 1.3:1, and mixed evenly, placed in flowing nitrogen or argon In an inert atmosphere such as gas, reach the required temperature of 500-1000°C at a heating rate of 1-30°C/min, and keep warm for 0.5-6 hours. Then program temperature control cooling or natural cooling to room temperature with power off. Or weigh and proportion silicon oxide, Mg and balls, put the mixture into a ball mill jar, and perform high-energy ball milling under an inert atmosphere. Ball milling time is 0.5 to 100 hours. The invention has the advantages of low raw material cost, simple process, less time-consuming, high yield, and the product has good capacity and cycle performance.
Description
Technical field
The invention belongs to technical field of lithium ion, a kind of preparation method who is used for silicon-based anode material of lithium-ion battery is provided.
Background technology
Mobile communication, laptop computer and digital vedio recording are three industries with fastest developing speed in the current global electronic information industry, along with developing rapidly of these industries, as the lithium ion battery of one of these three main accessories of leading products, undoubtedly also become a rising industry that has future.Compare with traditional Ni/Cd, Ni/MH battery, advantages such as lithium ion battery has energy density height, operating voltage height, load characteristic is good, charging rate is fast, safety non-pollution are a kind of secondary cells with fastest developing speed at present, that market prospects are the brightest.
Adopt lithium transition-metal oxide/graphite system in the present business-like lithium ion battery mostly, but limited by the theoretical lithium storage content of this system electrode itself (as graphite, 372mAh/g, 855mAh/cm
3), improve battery performance by the improvement battery preparation technique merely and be difficult to make a breakthrough, for satisfying the demand of high-capacity lithium ion cell, research and development height ratio capacity lithium ion battery electrode material is very urgent and necessary.
In the research of anticathode material, it is found that some alloy cpd may become the research new approaches of lithium ion battery negative material.All have higher lithium storage content as Si, Ge, Sn, Pb, Al, Ga, Sb etc., therefore, alloy material becomes the candidate target of new type lithium ion battery negative material.But alloy material has a very big shortcoming, in charge and discharge process, can be attended by very large change in volume, this huge change in volume easily causes the material efflorescence, make some particle lose contact each other, even come off from electrode matrix, finally cause electrode capacity to reduce the lost of life.In order to improve and to improve the life-span of alloy material of cathode, the change in volume that the mitigation lithium takes off in the embedding process is a key point.One of them feasible solution be exactly can with the metal of lithium height chemical combination in introduce the component of the relatively poor or even inertia of relative activity, serve as buffering " matrix " cushioning the change in volume of electrode in the charge and discharge process, thereby keep the structural stability of material.
The theoretical lithium storage content of Si is 4200mAh/g, approach carbon negative pole material ten times.Yet the negative pole by pure Si powder constituent will be followed bigger change in volume in the removal lithium embedded process, thereby influence the cyclical stability of electrode.Studies show that can the volumetric expansion of buffer Si powder in the removal lithium embedded process with the composite electrode of Si and inert base composition.The source of inert base, kind, character, and the correlation of inert base and Si had a strong impact on the chemical property of silicon based composite material, as specific capacity, cycle performance and high rate performance.With low cost in view of silicon; specific capacity is high; therefore, research and develop that a kind of production cost is low, technology is simple, productive rate is high, be convenient to the synthetic method of silicon-based anode material of large-scale production for promoting the practical application of silicon-based anode material in lithium ion battery to have crucial meaning.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of silicon-based anode material of lithium-ion battery.Realized that production cost is low, technology is simple, the process characteristic that productive rate is high; The uniform particles of synthetic silicon-based anode material powder is tiny, specific capacity height, stable cycle performance.
The present invention adopts magnesium reduction process synthesis of silica-base anode material, utilizes the oxide of magnesium powder as reducing agent reduction silicon, preparation silicon/magnesium oxide anode material, and concrete preparation technology is as follows:
The oxide powder of micron order, submicron order or nanoscale magnesium powder and silicon is carried out the weighing proportioning, and the addition of the oxide of magnesium powder and silicon was calculated according to the Mg/O atomic ratio in 0.1: 1～1.3: 1.
Adopt mechanical dry to mix or after the method for wet mixing mixes it, place inert atmospheres such as flowing nitrogen or argon gas, reach temperature required 500～1000 ℃, be incubated 0.5～6 hour, be cooled to room temperature then with the heating rate of 1～30 ℃/min.Perhaps adopt high-energy ball milling method directly to produce the Si/MgO anode material, ratio of grinding media to material 1: 1～50: 1,100～3000 rev/mins of rotating speeds, 0.5～100 hour ball milling time.
The oxide of described silicon is SiO or SiO
2
According to calculation of thermodynamics, some oxides of silicon can be reduced at normal temperatures by magnesium metal.Consider that from the dynamics angle reaction need be carried out at a certain temperature.Because the oxide of silicon generates elemental silicon after by magnesium-reduced, magnesium then is oxidized to magnesium oxide, magnesium oxide can prevent the volumetric expansion of elemental silicon in the removal lithium embedded process effectively, prevents the reunion of elemental silicon in course of reaction simultaneously, thereby can obtain good cyclical stability.
The invention has the advantages that: cost of material is low, technical process is simple, and has good electrochemical, and specific discharge capacity is up to 1350mAh/g, and stable cycle performance still can obtain the reversible specific capacity of 1000mAh/g in 5 circulations.
Description of drawings
Fig. 1 is the XRD figure of the synthetic Si/MgO anode material of magnesiothermic reduction of the present invention.SiO
2With the molar ratio of Mg be 1: 2, with SiO
2Mix the back calcining with Mg and obtain, 5 ℃/min of heating rate, synthesis temperature are 700 ℃, temperature retention time 2 hours.
Fig. 2 is the XRD figure of the synthetic Si/MgO anode material of magnesiothermic reduction of the present invention.SiO
2With the molar ratio of Mg be 1: 2, with SiO
2Obtain ratio of grinding media to material 20: 1,500 rev/mins of rotating speeds, 2 hours ball milling time with the Mg high-energy ball milling method.
Fig. 3 is the specific capacity-cycle-index curve of the synthetic Si/MgO anode material of magnesiothermic reduction of the present invention.SiO
2, Mg molar ratio be 1: 2, with SiO
2Mix the back calcining with Mg and obtain, 5 ℃/min of heating rate, synthesis temperature are 700 ℃, temperature retention time 2 hours.
Embodiment
Embodiment 1:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 2 in molar ratio, after mixture is mixed, place that the heating rate with 5 ℃/min is elevated to 700 ℃ under the mobile argon gas atmosphere, be incubated 2 hours, outage naturally cools to room temperature then.The XRD material phase analysis result (shown in Figure 1) of gained sample shows that synthetic product is Si, MgO and a spot of Mg
2Si and MgSiO
3, Mg
2SiO
4, do not have the existence of other oxide impurity phases.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO composite negative pole material of preparation is about 1350mAh/g, and the charge ratio capacity is 1050mAh/g, and the charge ratio capacity of preceding 5 circulations as shown in Figure 3.
Embodiment 2:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 2 in molar ratio, and mixture is put into ball grinder, and the mass ratio of ball and mixture 20: 1 carried out high-energy ball milling 2 hours under inert atmosphere, 500 rev/mins of rotating speeds.The XRD material phase analysis result (shown in Figure 2) of gained sample shows that synthetic product is mainly Si, MgO.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO composite negative pole material of preparation is 1300mAh/g, and the charge ratio capacity is 1100mAh/g.
Embodiment 3:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 2 in molar ratio, after mixture is mixed, place that the heating rate with 1 ℃/min is elevated to 650 ℃ under the mobile argon gas atmosphere, be incubated 4 hours, outage naturally cools to room temperature then.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO composite negative pole material of preparation is about 1290mAh/g, and the initial charge specific capacity is 980mAh/g.
Embodiment 4:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 2 in molar ratio, and mixture is put into ball grinder, and the mass ratio of ball and mixture 5: 1 carried out high-energy ball milling 4 hours under inert atmosphere, 1000 rev/mins of rotating speeds.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO composite negative pole material of preparation is about 1340mAh/g, and the initial charge specific capacity is 1060mAh/g
Embodiment 5:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 2 in molar ratio, after mixture is mixed, place that the heating rate with 2 ℃/min is elevated to 900 ℃ under the mobile argon gas atmosphere, be incubated at 4 o'clock, outage naturally cools to room temperature then.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO anode material of preparation is about 1300mAh/g, and the charge ratio capacity is 1010mAh/g.
Embodiment 6:
With SiO
2(〉=98.5%) and Mg (＞99.0%) are initial feed, prepare burden in 1: 1.6 in molar ratio, after mixture is mixed, place that the heating rate with 5 ℃/min is elevated to 700 ℃ under the mobile argon gas atmosphere, be incubated at 2 o'clock, outage naturally cools to room temperature then.
Synthetic product, conductive agent acetylene black, binding agent PVDF are pressed mass ratio to be mixed at 75: 15: 15, add an amount of NMP and make slurry, evenly be applied on the Copper Foil, cut into circular pole piece after the oven dry, form Experimental cell with lithium metal and carry out the constant current charge-discharge experiment, charging and discharging currents is 100mA/g, and the charging/discharging voltage scope is controlled between the 0.01-1.5V.The first discharge specific capacity of the Si/MgO anode material of preparation is about 1210mAh/g, and the charge ratio capacity is 940mAh/g.
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| CN114373915B (en) * | 2022-01-12 | 2024-02-02 | 万华化学集团股份有限公司 | Silicon oxide negative electrode material and preparation method thereof |
| CN115799464A (en) * | 2022-09-27 | 2023-03-14 | 重庆长安新能源汽车科技有限公司 | Lithium battery negative electrode material and preparation method and application thereof |
| CN115954558A (en) * | 2022-11-29 | 2023-04-11 | 蚌埠学院 | Aqueous ion secondary battery |
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| US6638662B2 (en) * | 1999-02-23 | 2003-10-28 | Hitachi, Ltd. | Lithium secondary battery having oxide particles embedded in particles of carbonaceous material as a negative electrode-active material |
| CN1601786A (en) * | 2003-09-26 | 2005-03-30 | 中国科学院物理研究所 | Oxygen-containing composite carbon material for secondary lithium battery and its preparation method and use |
| CN1661833A (en) * | 2004-02-25 | 2005-08-31 | 三星Sdi株式会社 | Negative electrode active material for rechargeable lithium battery, preparation method thereof, and rechargeable lithium battery containing it |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6638662B2 (en) * | 1999-02-23 | 2003-10-28 | Hitachi, Ltd. | Lithium secondary battery having oxide particles embedded in particles of carbonaceous material as a negative electrode-active material |
| CN1601786A (en) * | 2003-09-26 | 2005-03-30 | 中国科学院物理研究所 | Oxygen-containing composite carbon material for secondary lithium battery and its preparation method and use |
| CN1661833A (en) * | 2004-02-25 | 2005-08-31 | 三星Sdi株式会社 | Negative electrode active material for rechargeable lithium battery, preparation method thereof, and rechargeable lithium battery containing it |
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