CN102208632A - Silicon nano wire-fullerene complex cathode material for lithium ion battery and preparation method thereof - Google Patents
Silicon nano wire-fullerene complex cathode material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon nano wire-fullerene complex cathode material for a lithium ion battery and a preparation method thereof. Fullerene flexible conductive particles and silicon nano wires form a binary complex together; and the silicon nano wires are used as a main body for storing lithium, and the fullerene flexible conductive particles are supported on the surfaces of the silicon nano wires to form a topological netlike structure consisting of silicon nano wire arrays and fullerene. According to the topological netlike structure characteristics of the silicon nano wire-fullerene complex cathode material for the lithium ion battery, in the complex structure, the flexible conductive fullerene supported granules have double functions, wherein on one hand, volume expansion of silicon in the lithium embedding process can be buffered by a large amount of gaps among the fullerene and excellent elasticity of the fullerene so as to block the fusion of the adjacent silicon nano wires; and on the other hand, the fullerene can be used as a connector of the silicon nano wires to realize multi-channel migration of lithium ions, so the complex cathode material has more excellent cyclical stability and charge/discharge performance compared with the traditional silicon cathode material.
Description
Technical field
The present invention relates to the invention provides a kind of novel lithium ion battery with silicon nanowires-fullerene synthesis negative material and preparation method thereof, belong to the lithium ion battery field.
Background technology
Lithium ion battery have operating voltage height, specific capacity big, have extended cycle life, security performance is good, memoryless, non-environmental-pollution, self discharge is little and can fast charging and discharging etc. plurality of advantages, science and technology that has become that countries in the world pay close attention to and industry focus.Can one of key issue of research and development new type lithium ion battery be design and produce the negative material of excellent performance.Silicon materials are considered to one of most promising high-performance lithium cell negative electrode material, its the highest theoretical capacity is 4200mAh/g, surpass 10 times at conventional graphite electrode, specific capacity much larger than various nitride and oxide, and Si is difficult for causing the formation of Li dendrite at electrode surface in charge and discharge process, safe, also have simultaneously and advantages [Small 5,2236-2242 (2009)] such as the electrolyte reactivity is low.
Yet the volumetric expansion up to 300% can take place in the silicon-based anode material in charge and discharge process, causes the broken and battery capacity decline of silica flour, makes its application in lithium ion battery be subjected to very big restriction [J.Power Sources 81,233-236 (1999)].Therefore, how not only to keep the high power capacity of silicon but also can improve the research emphasis that its cyclical stability is current silica-base material, important effect is played in the development of lithium ion battery negative material.At present, solution silicon mainly contains the amorphous silica-base film of preparation, preparation porous silica material, preparation silicon nanowires and preparation silicon based composite material etc. as the method for the cyclical stability of lithium ion battery negative material.But this several method is all because the restriction of various factors causes the lithium battery decreased performance: low as amorphous silicon base film cycle-index under big capacity; The porous silicon structure repeatedly can caved in after the circulation, and tiny cavity disappears; The poorly conductive of silicon nanowires and lithium ion migrating channels block easily; Silicon grain is reunited easily etc. in the silicon based composite material.
Preparation silicon nanowires composite material also is considered to solve the effective way of silica-based lithium ion battery.People such as Wen Zhongsheng [Wen Zhongsheng, Deng. number of patent application: 201010223672.0] silicon and gold grain are filled in the silicon nanowires, the good electric conductivity of gold has well improved the electrical contact performance of silicon nanowires, but gold grain self does not store up the lithium ability, has reduced the specific capacity of composite material.
Summary of the invention
The object of the present invention is to provide a kind of silicon nanowires with high power capacity and high cyclical stability-fullerene synthesis structure that can be used as lithium ion battery negative material and preparation method thereof.
The objective of the invention is to realize in the following way:
A kind of lithium ion battery silicon nanowires-fullerene synthesis negative material, fullerene compliant conductive particle and silicon nanowires are formed binary synthesis complex jointly; Fullerene compliant conductive particulate load forms a topological network structure that is made of silicon nanowire array and fullerene at surface of silicon nanowires;
The mass percent of fullerene compliant conductive particle is between 0.5%～40% in the described synthesis negative material.
A kind of lithium ion battery preparation method of silicon nanowires-fullerene synthesis negative material specifically may further comprise the steps:
1) adopts metal catalytic chemical corrosion technology, utilize the silicon chip of surface cleaning to prepare silicon nanowires;
2) silicon nanowires is inserted in the electrolyte of mixed liquor of the fullerene aggregation that has negative electrical charge and carry out electro-chemical deposition process;
3) electrochemical deposition obtains lithium ion battery silicon nanowires-fullerene synthesis negative material.
Described silicon chip is monocrystalline silicon, polysilicon, [111] type silicon chip, [100] type silicon chip, p type doped silicon wafer or n type doped silicon wafer.
The described mixed liquor that has the fullerene aggregation of negative electrical charge is made up of the mixing of fullerene toluene solution and acetonitrile, and both volume ratios are 1: 3-15, and the concentration of fullerene is 20～40 μ M;
Described electrochemical deposition condition is that deposition voltage is 10-500V; Sedimentation time is 1-60min.
Lithium ion battery is carried out annealing in process with silicon nanowires-fullerene synthesis negative material.
The present invention has following beneficial effect, the lithium ion battery topological netted architectural feature of silicon nanowires-fullerene synthesis negative material, and silicon nanowires wherein is as the main body of storage lithium, and the compliant conductive particle is as the chain junctor.In this synthesis structure, compliant conductive fullerene loaded particle has dual-use function: on the one hand because a large amount of spaces between the fullerene and the excellent resilience performance of fullerene can cushion the volumetric expansion of silicon in embedding lithium process, thereby hinder the fusion of adjacent silicon nano wire; Fullerene can serve as the connector of silicon nanowires on the other hand, realizes the multichannel migration of lithium ion.Thereby have with the traditional silicon negative material and compare more excellent cyclical stability and charge-discharge performance.Characteristics of the present invention also are among the preparation method in conjunction with fullerene electronegative and form the characteristics of aggregation in toluene and acetonitrile mixed solution, and the method by electrochemical deposition at room temperature loads to surface of silicon nanowires with fullerene.Method simple economy, adjustability height.
Description of drawings
Fig. 1 is the microstructure schematic diagram of lithium ion battery of the present invention with silicon nanowires-fullerene synthesis negative material.
Fig. 2 is the microstructure part enlarged diagram of lithium ion battery of the present invention with silicon nanowires-fullerene synthesis negative material.
Embodiment
As shown in Figure 1 and Figure 2: a kind of lithium ion battery is formed binary synthesis complex jointly with silicon nanowires-fullerene synthesis negative material, fullerene compliant conductive particle 2 and silicon nanowires 1; Silicon nanowires is as the main body of storage lithium, and fullerene compliant conductive particle 2 loads on silicon nanowires 1 surface, forms a topological network structure that is made of silicon nanowire array and fullerene; The mass percent of fullerene compliant conductive particle is between 0.5%～40% in the described synthesis negative material.
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm n type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 3
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 0.01-0.2 Ω * cm p type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 4
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 30min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 5
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type polysilicon chip
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 6
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type [111] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 7
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; Be coated with one deck plastic cement on the not burnishing surface of silicon chip, the method with electroless deposition deposits one deck nano-Ag particles film on silicon chip again, and electroplate liquid is HF and the 0.005M AgNO of 4.8M
3Mixed solution, the time is 1.5min; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; Silicon chip after the corrosion is inserted in the acetone soln, and the plastic cement until the silicon chip back side comes off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 20 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 20min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Embodiment 8
Silicon chip is cleaned up; With resistivity is that to be immersed in volume ratio be 1: 3 30%H to 3-7 Ω * cm p type [100] direction monocrystalline silicon piece
2O
2: dense H
2SO
4In the solution, soak time is about 20min; In 5% hydrofluoric acid solution, soak about 5min then; On the not burnishing surface of silicon chip, be coated with one deck plastic cement, the polystyrene sphere of a monolayer is laid in self assembly on burnishing surface, and the method etching bead with the reaction particle etching makes little bulb diameter diminish, form certain interval between the ball, and cross one deck silverskin living steaming of silicon chip with steaming the method for crossing; After silver-plated silicon chip utilized washed with de-ionized water, place 4.8M HF and 0.4M H
2O
2Mixed solution in, under 50 ℃ constant temperature, react 60min; With the corrosion after silicon chip place successively carbon trichloride and acetone soln and, the polystyrene sphere in cleaning silicon chip front and the plastic cement at the back side come off; Utilize HNO at last successively
3After solution, HF solution and the washed with de-ionized water, can obtain silicon nanowire array after the drying.
Get in the acetonitrile solution that the fullerene toluene solution joins 10 times of volumes, the concentration of modulation fullerene is to 30 μ M.As anode, electro-conductive glass carries out electrochemical deposition as negative electrode under the constant voltage of 200V with silicon nanowire array, sedimentation time is 5min, utilize acetonitrile, washed with de-ionized water successively, drying can obtain target product of the present invention, silicon nanowires-fullerene synthesis structure.
Claims (6)
1. a lithium ion battery is with silicon nanowires-fullerene synthesis negative material, and it is characterized in that: fullerene compliant conductive particle (2) and silicon nanowires (1) are formed binary synthesis complex jointly; Fullerene compliant conductive particle (2) loads on silicon nanowires (1) surface, forms a topological network structure that is made of silicon nanowire array and fullerene;
The mass percent of fullerene compliant conductive particle is between 0.5%～40% in the described synthesis negative material.
2. a kind of lithium ion battery according to claim 1 preparation method of silicon nanowires-fullerene synthesis negative material is characterized in that:
Specifically may further comprise the steps:
1) adopts metal catalytic chemical corrosion technology, utilize the silicon chip of surface cleaning to prepare silicon nanowires;
2) silicon nanowires is inserted in the electrolyte of mixed liquor of the fullerene aggregation that has negative electrical charge and carry out electro-chemical deposition process;
3) electrochemical deposition obtains lithium ion battery silicon nanowires-fullerene synthesis negative material.
3. a kind of lithium ion battery according to claim 2 is characterized in that with the preparation method of silicon nanowires-fullerene negative material described silicon chip is for being monocrystalline silicon, polysilicon, [111] type silicon chip, [100] type silicon chip, p type doped silicon wafer or n type doped silicon wafer.
4. a kind of lithium ion battery according to claim 2 preparation method of silicon nanowires-fullerene negative material, it is characterized in that the described mixed liquor that has the fullerene aggregation of negative electrical charge is made up of the mixing of fullerene toluene solution and acetonitrile, both volume ratios are 1: 3-15, the concentration of fullerene is 20～40 μ M.
5. a kind of lithium ion battery according to claim 2 is characterized in that with the preparation method of silicon nanowires-fullerene negative material described electrochemical deposition condition is that deposition voltage is 10-500V; Sedimentation time is 1-60min.
6. a kind of lithium ion battery according to claim 2 is characterized in that lithium ion battery is carried out annealing in process with silicon nanowires-fullerene synthesis negative material with the preparation method of silicon nanowires-fullerene negative material.
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Cited By (11)
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| CN102800850A (en) * | 2012-08-02 | 2012-11-28 | 上海交通大学 | Method used for preparing silicon substrate three-dimensional nanometer structure through substep heating |
| CN103875100A (en) * | 2011-10-17 | 2014-06-18 | 日产自动车株式会社 | Electrical-device-use negative-electrode active substance |
| CN104051791A (en) * | 2014-06-23 | 2014-09-17 | 中国科学院半导体研究所 | Preparation method of polycrystalline silicon-based nano-structure lithium battery |
| CN105449173A (en) * | 2014-08-29 | 2016-03-30 | 国家纳米科学中心 | Cavity-structuralized silicon-carbon core-shell nanowire array, and preparation method and use thereof |
| CN107078348A (en) * | 2014-07-22 | 2017-08-18 | 瑞克锐斯株式会社 | Minicell and the PCB substrate and semiconductor chip using it |
| CN108448059A (en) * | 2018-04-17 | 2018-08-24 | 星恒电源股份有限公司 | A kind of lithium ion battery silicium cathode and preparation method thereof |
| CN110010864A (en) * | 2019-03-21 | 2019-07-12 | 中国科学院半导体研究所 | Silicon-graphene battery negative electrode material and preparation method thereof, lithium battery |
| US11005097B2 (en) | 2012-08-21 | 2021-05-11 | Kratos LLC | Group IVA functionalized particles and methods of use thereof |
| CN115188947A (en) * | 2022-07-13 | 2022-10-14 | 河南工业大学 | One-dimensional silicon-based composite negative electrode material, negative electrode plate comprising same, electrochemical device and electronic device |
| US11522178B2 (en) | 2016-07-05 | 2022-12-06 | Kratos LLC | Passivated pre-lithiated micron and sub-micron group IVA particles and methods of preparation thereof |
| US11637280B2 (en) | 2017-03-31 | 2023-04-25 | Kratos LLC | Precharged negative electrode material for secondary battery |
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| CN103875100A (en) * | 2011-10-17 | 2014-06-18 | 日产自动车株式会社 | Electrical-device-use negative-electrode active substance |
| CN103875100B (en) * | 2011-10-17 | 2017-02-22 | 日产自动车株式会社 | Electrical-device-use negative-electrode active substance |
| CN102800850A (en) * | 2012-08-02 | 2012-11-28 | 上海交通大学 | Method used for preparing silicon substrate three-dimensional nanometer structure through substep heating |
| CN102800850B (en) * | 2012-08-02 | 2014-10-15 | 上海交通大学 | Method used for preparing silicon substrate three-dimensional nanometer structure through substep heating |
| US11005097B2 (en) | 2012-08-21 | 2021-05-11 | Kratos LLC | Group IVA functionalized particles and methods of use thereof |
| CN104051791A (en) * | 2014-06-23 | 2014-09-17 | 中国科学院半导体研究所 | Preparation method of polycrystalline silicon-based nano-structure lithium battery |
| CN107078348A (en) * | 2014-07-22 | 2017-08-18 | 瑞克锐斯株式会社 | Minicell and the PCB substrate and semiconductor chip using it |
| US10418661B2 (en) | 2014-07-22 | 2019-09-17 | Rekrix Co., Ltd. | Micro-battery, and PCB and semiconductor chip using same |
| CN105449173B (en) * | 2014-08-29 | 2019-04-12 | 国家纳米科学中心 | A kind of cavity structure silico-carbo core-shell nano linear array, preparation method and its usage |
| CN105449173A (en) * | 2014-08-29 | 2016-03-30 | 国家纳米科学中心 | Cavity-structuralized silicon-carbon core-shell nanowire array, and preparation method and use thereof |
| US11522178B2 (en) | 2016-07-05 | 2022-12-06 | Kratos LLC | Passivated pre-lithiated micron and sub-micron group IVA particles and methods of preparation thereof |
| US11637280B2 (en) | 2017-03-31 | 2023-04-25 | Kratos LLC | Precharged negative electrode material for secondary battery |
| CN108448059A (en) * | 2018-04-17 | 2018-08-24 | 星恒电源股份有限公司 | A kind of lithium ion battery silicium cathode and preparation method thereof |
| CN110010864A (en) * | 2019-03-21 | 2019-07-12 | 中国科学院半导体研究所 | Silicon-graphene battery negative electrode material and preparation method thereof, lithium battery |
| CN115188947A (en) * | 2022-07-13 | 2022-10-14 | 河南工业大学 | One-dimensional silicon-based composite negative electrode material, negative electrode plate comprising same, electrochemical device and electronic device |
| CN115188947B (en) * | 2022-07-13 | 2024-09-27 | 河南工业大学 | One-dimensional silicon-based composite anode material, anode piece containing anode material, electrochemical device and electronic device |
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Application publication date: 20111005 |