CN102593439B - Silicon-based composite material for lithium ion battery and preparation method of silicon-based composite material - Google Patents
Silicon-based composite material for lithium ion battery and preparation method of silicon-based composite material Download PDFInfo
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- CN102593439B CN102593439B CN201210065826.7A CN201210065826A CN102593439B CN 102593439 B CN102593439 B CN 102593439B CN 201210065826 A CN201210065826 A CN 201210065826A CN 102593439 B CN102593439 B CN 102593439B
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- Y02E60/10—Energy storage using batteries
Abstract
A silicon-based composite material for a lithium ion battery and a preparation method of the silicon-based composite material belong to the technical field of cathode materials of lithium ion batteries. The composite material is marked as SI-M-C and comprises nano silicon, un-graphitized carbon and metal as well as trace amount of N element, S element and Na element. The preparation method of the silicon-based composite material includes the following steps: carrying out ultrasound diffusion on silicon powder, metal phthalocyanine, pyrazine and sodium lauryl sulfate in N,N-dimethyl formamide solvent; then transferring the obtained liquid into an automatic pressure reaction kettle with a polytetrafluoroethylene inner container for heating; carrying out vacuum rotary steaming on a thermal polymerization product to remove an organic solvent; and drying the obtained powder in a vacuum drying box and then thermally treating the solid powder under the protection of an argon gas atmosphere and finally obtaining a Si-M-C compound. Under the conditions that the voltage is positioned within 0.05-3.0V and the charge-discharge rate is 100mAg<-1>, the stable reversible specific capacity of the prepared composite material can reach over 700mAg<-1> to the minimized extent; and the silicon-based composite material has better application prospect.
Description
Technical field
The invention belongs to lithium ion battery material field, be specifically related to a kind of silicon based anode material and preparation method thereof.
Background technology
Operating voltage is high because having for lithium ion battery, specific energy is large, memory-less effect and environmental pollution is little etc. that advantage becomes one of focus of energy field research and development.Along with society and scientific and technological development, people have higher requirement to the performance of lithium ion battery, and electrode material plays key effect in battery performance improves.Commercialization negative pole is mainly graphite type material at present, and its theoretical capacity only has 372mAhg
-1, during practical application, capacity can be lower.In this case, research research has the more lithium ion battery negative material of high power capacity and better cycle performance and is significant.
Si can form Li with Li
22si
5alloy, theoretical capacity can reach 4200mAhg
-1, far away higher than graphite cathode; Silicon is to Li
+the current potential average out to 0.25V of/Li, can guarantee the high voltage of battery with positive pole pairing; Moreover the reserves of silicon are abundant, and environmentally friendly.Therefore silicon is a kind of very promising lithium ion battery negative material.Yet silicon is in charge and discharge cycles, and violent variation can occur volume, destroy the structure of material, cause the pulverizing of electrode, thereby cause electrode cycle performance to worsen.On the other hand, the efficiency first of silicium cathode is conventionally very low, has limited the application of its reality.At present, what in document, conventionally adopt improves silicon electrode chemical property method and can be divided into two classes: the one, by silicon and carbon compound use, utilize carbon-coating as protective layer and buffering matrix, suppress the reunion of silicon and cushion its change in volume, thereby maintaining the cyclical stability of electrode; The 2nd, the metal-doped conductive network that provides is provided, thereby improve silicon, react with the charge transfer of lithium, to strengthen the chemical property of silicon electrode.
Yet, method such as the arc discharge of traditional carbon coated Si, laser deposition, chemical vapour deposition (CVD) etc., normally used equipment is complicated, and power consumption is large, cost is high, complex operation, is difficult to realize large-scale production.Other carbon source is poisonous organic reagent, and operating condition requires high, easily causes environmental pollution.And although the simple metal-doped conductivity that improves electrode often can not obtain good cycle performance.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide that a kind of efficiency is first high, specific capacity is high, the silicon based composite material of good cycling stability and prepare the method for this material.
Lithium ionic cell cathode silicon based compound material prepared by the present invention, be labeled as Si-M-C, mainly comprise nano-silicon, ungraphitised carbon and metal, the mass content of silicon in composite material is in 20%～60% scope, and containing micro-N, S and Na element, the mass ratio of these three kinds of elements in composite material is less than 1%.Wherein, the average grain diameter of silicon is 50nm, for main doff lithium active material, is dispersed in non-graphitized carbon-coating; Ungraphitised carbon had both belonged to active material, and the change in volume during again to silicon doff lithium plays cushioning effect; M is Co, Fe or Mn, and existence form is metal simple-substance or Si-M alloy, has improved the conductivity of electrode.
The preparation method of Si-M-C composite material provided by the invention, specifically comprises the following steps:
1) silica flour and metal phthalocyanine are mixed according to certain mass ratio, and add a certain amount of pyrazine and lauryl sodium sulfate, ultrasonic being dispersed in DMF solvent;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 150 ℃～180 ℃ baking ovens and is incubated 3～6 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 600 ℃-800 ℃, finally obtains Si-M-C compound.
Wherein, step 1) silicon described in is nano silica fume, and average grain diameter is 50nm; Metal phthalocyanine is a kind of in iron-phthalocyanine, cobalt phthalocyanine or manganese phthalocyanine; The purity of metal phthalocyanine is more than 90%; The mass ratio of silica flour and metal phthalocyanine is between 1: 2～1: 8; The mol ratio of metal phthalocyanine and pyrazine is 1: 2; The mol ratio of metal phthalocyanine and lauryl sodium sulfate is 10: 1.Step 4) purity of argon described in is more than 99%.
Compared with prior art, the present invention has the following advantages:
1) in the prepared Si-M-C composite material of the present invention, the combination of Si and metal and C thereof is more firm, when making conductive network that S i had, in the buffering matrix being present in again, has guaranteed that composite material has good chemical property; If prepared composite material is in the voltage range of 0.05V～3.0V, 100mAg
-1charge-discharge magnification under, the minimum 700mAhg that reaches of its stable reversible specific capacity
-1above, there is good application prospect.
2) to prepare the process of Si-M-C composite material simple in the present invention, and the coated step of the metal-doped and carbon of silicon is realized, and is suitable for large-scale production.
Accompanying drawing explanation
The X-ray diffractogram of prepared sample and business nano silica fume in Fig. 1, embodiment 1,2,3;
The transmission electron microscope picture of prepared sample and business nano silica fume in Fig. 2, embodiment 1,2,3;
(a) Si; (b) Si-Co-C; (c) Si-Fe-C and (d) Si-Mn-C;
The charge-discharge performance figure of prepared sample and business nano silica fume in Fig. 3, embodiment 1,2,3;
The charge-discharge performance figure of prepared sample in Fig. 4, embodiment 4.
Embodiment
Embodiment 1
1) weigh respectively approximately 0.11 gram of silica flour, 0.55 gram of Cobalt Phthalocyanine, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 160 ℃ of baking ovens and is incubated 4.5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 700 ℃, finally obtains Si-Co-C compound.
Embodiment 2
1) weigh respectively approximately 0.11 gram of silica flour, 0.55 gram of FePC, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 160 ℃ of baking ovens and is incubated 4.5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 700 ℃, finally obtains Si-Fe-C compound.
Embodiment 3
1) weigh respectively approximately 0.11 gram of silica flour, 0.55 gram of manganese phthalocyanine, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 160 ℃ of baking ovens and is incubated 4.5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 700 ℃, finally obtains Si-Mn-C compound.
Embodiment 4
1) weigh respectively approximately 0.07 gram of silica flour, 0.56 gram of Cobalt Phthalocyanine, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 160 ℃ of baking ovens and is incubated 5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 700 ℃, finally obtains Si-Co-C compound
Embodiment 5
1) weigh respectively approximately 0.55 gram of 0.11 gram of silica flour, FePC, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 180 ℃ of baking ovens and is incubated 4.5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 700 ℃, finally obtains Si-Fe-C compound.
Embodiment 6
1) weigh respectively approximately 0.11 gram of silica flour, 0.55 gram of manganese phthalocyanine, 0.16 gram of pyrazine and 0.028 gram of dodecyl sodium sulfate and be dissolved in the DMF of 35mL, ultrasonic agitation 60 minutes;
2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 160 ℃ of baking ovens and is incubated 4.5 hours;
3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
4) by step 3) in gained pressed powder under argon gas atmosphere protection, heat-treat 1h, temperature is 800 ℃, finally obtains Si-Mn-C compound
Fig. 1 is the X ray diffracting spectrum of prepared sample and business nano silica fume in embodiment 1,2,3.As can be seen from the figure, the characteristic diffraction peak of silicon has six, and 2 θ values are respectively 28.6 °, 47.5 °, 56.2 °, 69.3 °, 76.6 ° and 88.2 °.The wide diffraction maximum correspondence of △ mark ungraphitised carbon; * the diffraction maximum correspondence of mark Co; ◆ the diffraction maximum correspondence of mark Fe
2si;
the diffraction maximum correspondence of mark MnSi.
Fig. 2 is the transmission electron microscope picture of prepared sample and business nano silica fume in embodiment 1,2,3.As can be seen from the figure, Si nano particle is embedded in the carbon-coating of prepared Si-M-C composite material dispersedly.
The silicon based composite material that the present invention makes and adopt CR2032 type button cell carrying out on new prestige tester as the chemical property evaluation of the business silica flour of reference.In electrode preparation, gained Si-M-C material (or business silica flour), carbon black (Super P) and sodium alginate are coated on stainless steel collector according to 70: 20: 10 even mixed pulps of mass ratio, then at the dry 12h of 80 ℃ of vacuum drying ovens.(it is following that water oxygen content all remains on 0.5ppm) carried out in being assemblied in the glove box that is full of argon gas of button cell, and metal lithium sheet, as to electrode and reference electrode, contains 1M LiPF
6eC/DMC (1: 1wt%) as electrolyte, Whatman GF/D borosilicate glass fiber filter paper is as barrier film.
Fig. 3 is the charge-discharge performance figure of prepared sample and business nano silica fume in embodiment 1,2,3.As can be seen from the figure, compare with business silica flour, Si-M-C composite material prepared by the present invention shows good cyclical stability, and can provide than the much higher specific capacity of commercial graphite carbon negative pole.
Fig. 4 is the charge-discharge performance figure of prepared sample in embodiment 4.As can be seen from Figure, at silica flour and the Cobalt Phthalocyanine mass ratio that feeds intake, be 1: 8 o'clock, in the voltage range of prepared composite electrode 0.05V～3.0V, 100mAg
-1charge-discharge magnification under, specific capacity 70 times circulation after still can remain on 700mAhg
-1above; The efficiency first of electrode is 65%, from circulation for the second time, starts to approach and remains on 100%.
Claims (3)
1. the preparation method of lithium ionic cell cathode silicon based compound material, described lithium ionic cell cathode silicon based compound material, be labeled as Si-M-C, mainly comprise nano-silicon, ungraphitised carbon and metal, the mass content of silicon in composite material is 20%～60%, the average grain diameter of silicon is 50nm, for main doff lithium active material, is dispersed in non-graphitized carbon-coating; Ungraphitised carbon had both belonged to active material, and the change in volume during again to silicon doff lithium plays cushioning effect; M is Co, Fe or Mn, and existence form is metal simple-substance or Si-M alloy, it is characterized in that, comprises the following steps:
(1) silica flour and metal phthalocyanine are mixed according to certain mass ratio, and add a certain amount of pyrazine and lauryl sodium sulfate, ultrasonic being dispersed in DMF solvent; The mass ratio of silica flour and metal phthalocyanine is between 1:2～1:8; The mol ratio of metal phthalocyanine and pyrazine is 1:2; The mol ratio of metal phthalocyanine and lauryl sodium sulfate is 10:1;
(2) step (1) gained liquid rotating is moved in the self-pressure reactor of polytetrafluoroethylliner liner, then reactor is placed in to 150 ℃～180 ℃ baking ovens and is incubated 3～6 hours;
(3) above-mentioned thermal polymerization product vacuum is revolved to steaming, remove organic solvent, then in 80 ℃ of vacuum drying ovens, dry;
(4) gained pressed powder in step (3) is heat-treated to 1h under argon gas atmosphere protection, temperature is 600 ℃-800 ℃, finally obtains Si-M-C compound.
2. according to the preparation method of claim 1, it is characterized in that, the silicon described in step 1) is nano silica fume, and average grain diameter is 50nm; Metal phthalocyanine is a kind of in iron-phthalocyanine, cobalt phthalocyanine or manganese phthalocyanine; The purity of metal phthalocyanine is more than 90%.
3. according to the preparation method of claim 1, it is characterized in that, the purity of argon described in step 4) is more than 99%.
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| US9337478B2 (en) * | 2012-02-14 | 2016-05-10 | Shailesh Upreti | Composite silicon or composite tin particles |
| JP5801775B2 (en) * | 2012-08-03 | 2015-10-28 | 信越化学工業株式会社 | Silicon-containing particles, negative electrode material for non-aqueous electrolyte secondary battery using the same, non-aqueous electrolyte secondary battery, and method for producing silicon-containing particles |
| CN103833076A (en) * | 2012-11-27 | 2014-06-04 | 王泰林 | Nickel oxide-titanium dioxide nano composite material |
| CN103682251B (en) * | 2013-12-10 | 2016-06-15 | 浙江大学 | A kind of porous iron sesquioxide/carbon nanosheet composite and preparation method thereof and its application in preparing lithium ion battery |
| CN104900843A (en) * | 2015-06-13 | 2015-09-09 | 田东 | Preparation method of silicon carbon composite anode material |
| CN105742589B (en) * | 2016-02-29 | 2018-09-18 | 中国有色桂林矿产地质研究院有限公司 | A kind of negative electrode of lithium ion battery silicon-cobalt-carbon composite and preparation method thereof |
| CN106941171B (en) * | 2017-04-26 | 2020-02-11 | 中能国盛动力电池技术（北京）股份公司 | Lithium battery cathode composite material based on nano silicon carbon and preparation method thereof |
| CN106920951B (en) * | 2017-04-26 | 2020-02-11 | 中能国盛动力电池技术（北京）股份公司 | Nano silicon-carbon composite material for lithium battery cathode and preparation method thereof |
| CN109103443B (en) * | 2018-08-08 | 2020-10-27 | 欣旺达电子股份有限公司 | Silicon-based negative electrode material and preparation method thereof |
| CN111354934B (en) * | 2020-03-23 | 2021-03-16 | 珠海冠宇电池股份有限公司 | Silicon-based negative electrode material and application thereof |
| CN113206231B (en) * | 2021-04-25 | 2022-06-10 | 浙江锂宸新材料科技有限公司 | Silicon-carbon-cobalt composite material and preparation method and application thereof |
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Non-Patent Citations (2)
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| 徐宇虹等.碳热还原法制备锂离子电池Si-Co-C复合负极材料.《2009年第十五次全国电化学学术会议论文集》.2009,第1页. |
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