CN103268933B - Al-Sn film negative electrode and preparation method thereof - Google Patents
Al-Sn film negative electrode and preparation method thereof Download PDFInfo
- Publication number
- CN103268933B CN103268933B CN201310163429.8A CN201310163429A CN103268933B CN 103268933 B CN103268933 B CN 103268933B CN 201310163429 A CN201310163429 A CN 201310163429A CN 103268933 B CN103268933 B CN 103268933B
- Authority
- CN
- China
- Prior art keywords
- substrate
- preparation
- pmma
- negative electrode
- adopting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Materials For Photolithography (AREA)
Abstract
The present invention discloses an Al-Sn film negative electrode and a preparation method thereof. The preparation method comprises the following steps: a, depositing an aluminum film on a brass substrate; b, adopting the sample obtained in the step a as a substrate, and adopting PMMA as an electron beam resist to prepare a hole array microstructure on the substrate; c, adopting PMMA as a protection layer, and carrying out an etching treatment on the sample obtained in the step b to obtain a hole array microstructure on the aluminum film; d, adopting the substrate with the microcosmic structure in the step c as a substrate, and adopting pure Sn as a target to deposit the pure Sn; and e, adopting hot acetone to remove the resist PMMA to obtain the Al-Sn film negative electrode. The method has advantages of designability, controllability, high flexibility and the like, wherein artificial control and design can be performed on Al-Sn distribution so as to buffer a volume expansion effect during a lithium ion battery charge and discharge reaction process and carry out quantitative analysis on volume structure change.
Description
Technical field
The present invention relates to the preparation method that a kind of micro-nano technology prepares lithium ion battery Al-Sn film negative electrode.
Background technology
In recent years, along with the development of micro-nano technology technology, microelectric technique and microsystems technology also enter nanoscale by micron order, and in the process, the development of various photoetching technique also serves very crucial effect.
The technology of new generation of electron beam exposure alternatively optical exposure, because its exposure low yield, until today, does not still enter large-scale production field.However, this technology has but entered other micro-nano technology fields gradually, and making optical mask is exactly the important commercial use of of electron beam exposure.In the epoch of nanometer technology today, the manufacturing process that electron beam exposure is indispensable especially.Utilize hyundai electronics bundle exposure sources and special resist technique can make the fine structure being less than 10nm, just because of the appearance of electron beam lithography, substantially reduce dimension of picture, the making of Micropicture and device more can be realized, thus promoting the development of nanosecond science and technology, its application is also obtain to expand greatly.And the flexibility of electron beam lithography and high-resolution also make it to become in scientific research institution the important tool studying micro-nano structure and device sex character.In field of material preparation, no matter be directly prepare material, or the object indirectly preparing material is reached by preparing masterplate, a kind of new approaches that the preparation be all the flexibility of electron sensitive resist being material provides, therefore, adopting electron beam lithography to prepare material is a kind of new method with designability, controllability.
Mutual insoluble alloy system Al-Sn has been proved to be the negative material (Ref:R.Z.Hu that can be used for as lithium ion battery, L.Zhang, et al.Electrochemistry Communications.2008, 10:1109-1112.), researcher is had to obtain Al-Sn film (Ref:Renzong Hu by the method for codeposition, Meiqin Zeng, et al.Journal of Power Sources.2009, 188:268-273.), the distribution of Al and Sn obtained does not in this way have rule, and Sn is easy to generate nano wire in deposition process, although final obtained material has good performance, but consider Li again
+diffusion rate in Al is less, and this will inevitably limit the capacity of Al-Sn film negative electrode and the further improvement of cycle performance, contributes to Li if therefore can design and prepare a kind of new microstructure
+diffusion in Al, and the Volumetric expansion of electrode material in charge and discharge process can also be slowed down, can better performance be obtained.
Summary of the invention
An object of the present invention is to provide a kind of Al-Sn film negative electrode with new microstructure.
Another object of the present invention is to provide a kind of preparation method of Al-Sn film negative electrode.
The object of the invention is to realize in the following manner:
A preparation method for Al-Sn film negative electrode, comprises the steps:
A, with latten(-tin) as substrate, by the method for vacuum magnetic-control sputtering deposition plating at deposition on substrate aluminium film;
B, using the sample that obtains in a step as substrate, take PMMA as electron sensitive resist, on substrate, prepare pores array micro-structural with electron beam lithography according to the figure designed;
C, be protective layer with PMMA, sample b step obtained utilizes tetramethylammonium hydroxide aqueous solution to carry out etching processing, and aluminium film obtains pores array micro-structural;
D, the substrate with microstructure that obtains in step c, as substrate, using pure Sn as target, again adopt the method for vacuum magnetic-control sputtering deposition plating, deposit pure Sn;
E, remove resist PMMA with hot acetone, thus obtain Al-Sn film negative electrode.
In step a and d, power and the control of time in vacuum magnetic-control sputtering deposition plating process need be considered, prevent excessively growing up of particle.Preferably, in step a and d, in vacuum magnetic-control sputtering deposition plating process, power is respectively 80 ~ 100W and 70 ~ 80W, and the time is respectively 15 ~ 20min and 10 ~ 15min.
Preferably, the mass fraction of described PMMA is 4%, and molecular weight is 350K.
Preferably, in step c, the mass concentration of described tetramethylammonium hydroxide aqueous solution is 20% ~ 30%, and etch period is 30s ~ 1min.
Preferably, step e removes PMMA and utilizes the acetone soak time 10 ~ 20min boiled, and is aided with ultrasonic cleaning 10 ~ 20min.
Above raw material, market is all on sale, and the present invention, all can implement without particular/special requirement brass and fine aluminium, pure tin.The Al-Sn alloy obtained has regular micro-structural alternately.
The present invention, compared with existing other lithium ion battery Al-Sn film negative electrode preparation method, has following beneficial effect:
(1) microstructure that the present invention adopts electron beam exposure to obtain has designability, can obtain the distribution of Al and Sn rule by this structure; The Al-Sn alloy that combination film deposition technique obtains has structure alternately, can effectively alleviate the Volumetric expansion of electrode material in discharge and recharge course of reaction, and in a big way, the structural stability of electrode material is improved.
(2) electron beam lithography of the present invention has good flexibility; can according to different requirements; the different structure of design preparation, and resist PMMA also can play a good template protection effect, for follow-up membrane-film preparation process provide convenient.
(3) method of the present invention can the effective amount of each position electrode material on control electrode sheet, the position relationship of each phase in alloy system electrode material can be set according to the figure of design, contribute to the volumetric expansion in lithium ion battery course of reaction, structural change is carried out determining quantitative analysis.In obtained membrane electrode, the position arrangement of Al, Sn as shown in Figure 5.
(4) Al-Sn of the present invention membrane electrode alternately, because the intercalation potential of Sn is higher than Al, when exoelectrical reaction, Sn is first reacting phase, and Al is the good conductivity of rear reacting phase, Al, but Li
+in Al, diffusion rate is lower, and diffusivity in Sn is better, and alternately, the Sn first reacted can provide more diffusion admittance for post-reacted Al to Al and Sn.
(5) Al-Sn of the present invention membrane electrode alternately, because Sn forms Li at embedding lithium
22sn
5time, its cubical expansivity is up to 260%, and the Al good material that is plasticity, just in time can absorb the STRESS VARIATION that Sn causes due to volumetric expansion.Al, Sn arrange regularly, be conducive to the change of Al-Sn structure evenly, avoid local stress concentrate.
(6) the present invention controls artificially the distribution of Al-Sn and designs the Volumetric expansion that both can delay and fill in lithium ion battery discharge and recharge course of reaction, can carry out determining quantitative analysis to volume structure change again.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 1 magnetron sputtering Al on brass base.
Fig. 2 is after embodiment 1 etches Al, the pores array figure on matrix.
Fig. 3 is the back scattering figure of the Al-Sn array after embodiment 1 hot acetone removal resist.
Fig. 4 is the schematic flow sheet of preparation method of the present invention.
Fig. 5 is the position arrangement schematic diagram of Al, Sn in the obtained membrane electrode of embodiment 1, and (a) is front schematic view, (b) side schematic view.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
According to the microstructure of invented Al-Sn membrane electrode, according to Al, the feature that Sn is insoluble mutually, design the array pattern of rule, consider the size of the Sn particle size obtained by vacuum magnetic-control sputtering film deposition techniques simultaneously, and the composition proportion problem of Al, Sn, the aperture size design in array pattern is at 500nm.Whole experimentation is matrix with latten(-tin), selects pure Al as target, utilizes vacuum magnetic-control sputtering to obtain Al film, and sputtering power is 100W, sputtering time 20min.Select mass fraction to be 4%, molecular weight be the PMMA of 350K as electron sensitive resist, with sol evenning machine be coated in Al film surface, on resist layer, obtain pattern through electron beam exposure.Again using PMMA as protective layer, select tetramethylammonium hydroxide aqueous solution etching Al, the soaking at room temperature 30s of 25%, cleaning, dry, realize pattern from resist layer to the transfer of Al film.Again adopt vacuum magnetic-control sputtering technology, using pure Sn as target, the Al film with array pattern of above-mentioned preparation deposits Sn, and sputtering power is 80W, sputtering time 15min.Finally utilize hot acetone to soak 15min, and ultrasonic cleaning 15min remove the PMMA resist layer between Al film and Sn film, obtains Al-Sn film negative electrode.
Utilize the membrane electrode of the above-mentioned preparation of scanning electronic microscope observation, Al and Sn in discovery electrode material alternately, reaches the set goal.
Claims (6)
1. a preparation method for Al-Sn film negative electrode, is characterized in that, comprises the steps:
A, with latten(-tin) as substrate, by the method for vacuum magnetic-control sputtering deposition plating at deposition on substrate aluminium film;
B, using the sample that obtains in a step as substrate, take PMMA as electron sensitive resist, be coated in aluminium film surface with sol evenning machine, on resist layer, prepare pores array micro-structural with electron beam lithography according to the figure designed;
C, be protective layer with PMMA, sample b step obtained utilizes tetramethylammonium hydroxide aqueous solution to carry out etching processing, and aluminium film obtains pores array micro-structural;
D, the substrate with microstructure that obtains in step c, as substrate, using pure Sn as target, again adopt the method for vacuum magnetic-control sputtering deposition plating, deposit pure Sn;
E, remove resist PMMA with hot acetone, thus obtain Al-Sn film negative electrode.
2. preparation method according to claim 1, is characterized in that, in step a and d, in vacuum magnetic-control sputtering deposition plating process, power is respectively 80 ~ 100W and 70 ~ 80W, and the time is respectively 15 ~ 20min and 10 ~ 15min.
3. preparation method according to claim 1 and 2, is characterized in that, the mass fraction of described PMMA is 4%, and molecular weight is 350K.
4. preparation method according to claim 1 and 2, is characterized in that, in step c, the mass concentration of described tetramethylammonium hydroxide aqueous solution is 20% ~ 30%, and etch period is 30s ~ 1min.
5. preparation method according to claim 1 and 2, is characterized in that, step e removes PMMA and utilizes the acetone boiled to soak 10 ~ 20min, and is aided with ultrasonic cleaning 10 ~ 20min.
6. the Al-Sn film negative electrode prepared of Claims 1 to 5 any one method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310163429.8A CN103268933B (en) | 2013-05-06 | 2013-05-06 | Al-Sn film negative electrode and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310163429.8A CN103268933B (en) | 2013-05-06 | 2013-05-06 | Al-Sn film negative electrode and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103268933A CN103268933A (en) | 2013-08-28 |
| CN103268933B true CN103268933B (en) | 2015-01-28 |
Family
ID=49012551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310163429.8A Active CN103268933B (en) | 2013-05-06 | 2013-05-06 | Al-Sn film negative electrode and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103268933B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103903970A (en) * | 2014-03-10 | 2014-07-02 | 中国科学院物理研究所 | Method for preparing heterogeneous electrode pair with nanometer gap |
| DE102015007291A1 (en) * | 2015-06-10 | 2016-12-15 | Forschungszentrum Jülich GmbH | Process for producing nanostructured layers |
| CN115275107B (en) * | 2022-09-28 | 2022-12-13 | 四川启睿克科技有限公司 | Silicon-based negative electrode with integrated structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101436656A (en) * | 2007-11-16 | 2009-05-20 | 比亚迪股份有限公司 | Lithium ion battery cathode and preparation method thereof and lithium ion battery |
| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
| CN102403420A (en) * | 2011-11-11 | 2012-04-04 | 哈尔滨工业大学深圳研究生院 | Preparation method for graphical sapphire substrate |
| CN102637852A (en) * | 2012-04-24 | 2012-08-15 | 浙江大学 | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100416094B1 (en) * | 2001-08-28 | 2004-01-24 | 삼성에스디아이 주식회사 | Anode thin film for Lithium secondary battery and preparation method thereof |
| JP2007012421A (en) * | 2005-06-30 | 2007-01-18 | Matsushita Electric Ind Co Ltd | Negative electrode for lithium ion battery and lithium ion battery using it |
-
2013
- 2013-05-06 CN CN201310163429.8A patent/CN103268933B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101436656A (en) * | 2007-11-16 | 2009-05-20 | 比亚迪股份有限公司 | Lithium ion battery cathode and preparation method thereof and lithium ion battery |
| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
| CN102403420A (en) * | 2011-11-11 | 2012-04-04 | 哈尔滨工业大学深圳研究生院 | Preparation method for graphical sapphire substrate |
| CN102637852A (en) * | 2012-04-24 | 2012-08-15 | 浙江大学 | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode |
Non-Patent Citations (2)
| Title |
|---|
| "High patternd cylindrical Ni-Sn alloys with 3-dimensionally ordered macroporous structure as anodes for lithium batteries";Sang-Wook Woo etal;《Electrochimica Acta》;20100206;第55卷;第8030-8035页 * |
| JP特开2007-12421A 2007.01.18 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103268933A (en) | 2013-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tippens et al. | Visualizing chemomechanical degradation of a solid-state battery electrolyte | |
| Ke et al. | Hierarchically bicontinuous porous copper as advanced 3D skeleton for stable lithium storage | |
| Liu et al. | Mechanically and chemically robust sandwich-structured C@ Si@ C nanotube array Li-ion battery anodes | |
| Karki et al. | Lithium-assisted electrochemical welding in silicon nanowire battery electrodes | |
| Gowda et al. | Three-dimensionally engineered porous silicon electrodes for Li ion batteries | |
| Choi et al. | Scalable fracture-free SiOC glass coating for robust silicon nanoparticle anodes in lithium secondary batteries | |
| Ye et al. | Lithium storage in bowl-like carbon: the effect of surface curvature and space geometry on Li metal deposition | |
| CN107623459B (en) | Friction nanometer power generator frictional layer surface roughening agrees with the preparation method of structure | |
| Xia et al. | Facile synthesis of free-standing silicon membranes with three-dimensional nanoarchitecture for anodes of lithium ion batteries | |
| Sandu et al. | Surface coating mediated swelling and fracture of silicon nanowires during lithiation | |
| CN103268933B (en) | Al-Sn film negative electrode and preparation method thereof | |
| CN102942178A (en) | Compound base of precious metal nanometer array and single layer graphene and preparation method thereof | |
| Polat et al. | Silicon-copper helical arrays for new generation lithium ion batteries | |
| Nam et al. | Probing the lithium ion storage properties of positively and negatively carved silicon | |
| CN107681122A (en) | A kind of three-dimensional grapheme Si MoS2The preparation method of composite | |
| CN103361601B (en) | A kind of method making surface enhanced Raman scattering substrate | |
| Qu et al. | High rate transfer mechanism of lithium ions in lithium–tin and lithium–indium alloys for lithium batteries | |
| CN109580723A (en) | A kind of preparation method and product of flexible humidity sensor | |
| CN104993115B (en) | A kind of lithium battery SiCO Si gradient films electrode systems and preparation method | |
| CN103682369A (en) | Lithium battery pole plate | |
| WO2023092799A1 (en) | Method and apparatus for marking internal micro-structure of electrochemical apparatus | |
| CN106803570B (en) | A kind of lithium battery SiCO- carbon nano-tube coextruded film electrode | |
| Wang et al. | Direct observation of nucleation and growth behaviors of lithium by in situ electron microscopy | |
| CN108108509A (en) | The reliable lossless operation of micro structures based on electrochemistry | |
| Tang et al. | Rapid and reversible Na deposition onto Al nanosheet arrays |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |