CN101719543A - Method for preparing silicon nanowire array membrane electrode - Google Patents
Method for preparing silicon nanowire array membrane electrode Download PDFInfo
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- CN101719543A CN101719543A CN200910024187A CN200910024187A CN101719543A CN 101719543 A CN101719543 A CN 101719543A CN 200910024187 A CN200910024187 A CN 200910024187A CN 200910024187 A CN200910024187 A CN 200910024187A CN 101719543 A CN101719543 A CN 101719543A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 127
- 239000010703 silicon Substances 0.000 title claims abstract description 127
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002070 nanowire Substances 0.000 title claims abstract description 98
- 239000012528 membrane Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 21
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 8
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910002796 Si–Al Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 21
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000004087 circulation Effects 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract 2
- 238000007747 plating Methods 0.000 abstract 1
- 235000012431 wafers Nutrition 0.000 abstract 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 238000005269 aluminizing Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000007 visual effect Effects 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a lithium ion battery anode with high performance, i.e. a method for preparing a silicon nanowire array membrane electrode, comprising the following steps of: catalyzing corroded silicon wafers by a metal, and corroding a monocrystalline silicon piece into a silicon nanowire array membrane completely consisting of the silicon nanowire through corrosion twice; and preparing into the electrode by using two different techniques, wherein two different techniques are as follows: 1, plating an aluminum membrane at the back side of the silicon nanowire array membrane by using a method of vacuum thermal evaporation; annealing to form an Si-Al alloy which is used as a current collector; and 2, covering a carbon aerogel on the surface of the silicon nanowire array membrane, pyrolyzing the carbon aerogel into the carbon through vacuum sintering and using the carbon aerogel as a current collector. The silicon nanowire array membrane is used as the lithium ion battery assembled with the anode and has the advantages of large lithium storage capacity, high Kulun efficiency, favorable circulation stability, convenient operation, and favorable repeatability without complicated apparatus.
Description
Technical field
The present invention relates to the preparation method of high performance lithium ion battery anode, particularly a kind of preparation method of high performance lithium ion battery anode-silicon nanowire array membrane electrode.
Background technology
Rechargeable lithium ion batteries is the current information-based visual plant that moves society.They are applied to portable electric appts, electric car and Medical Devices.One of main challenge of design electrode material is that the cycle performance that high lithium ion memory capacity is become reconciled is combined.Business-like graphitic carbon has good cycle performance, but low (the 372mAh g of capacity
-1).The lithium ion battery negative of silica-base material is owing to have high capacity (4200mAh g
-1) and be subjected to extensive concern.But silicon has experienced very big change in volume (＞300%) in charge and discharge process.So big change in volume can cause the electrode pulverizing and break away from current collector, and battery capacity is decayed fast.In order to improve battery life, some measures have been taked, such as the size that reduces material or use film or alloy.The cycle life of nano-silicon anode has improved, and this is because nano-silicon embeds and deviates from the globality that can hold big change in volume in the process and keep electrode at lithium ion.
The method of existing preparation silicon nanowire array has chemical vapour deposition technique, metal catalytic etch, template and photoetching process etc., but the silicon nanowire array of preparation is all in certain substrate, for example at the bottom of the silicon wafer-based or metallic substrates such as iron plate.People such as Peng Kuiqing use the silicon nanowires of metal catalytic etch preparation as the lithium ion battery anode, still, owing to kept the silicon chip of hundreds of micron thickness below the silicon nanowires, and so they can't get rid of the contribution of silicon chip antianode capacity.
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of high performance lithium ion battery anode-silicon nanowire array membrane electrode, prepared the back side and be wrapped up carbon-coating in silicon-aluminum layer or surface the silicon nanowire array film as the lithium ion battery anode, have make simple, volume is little, transmission property height, be fit to the characteristics produced in batches.
In order to achieve the above object, technical scheme of the present invention is achieved in that the preparation method of silicon nanowire array membrane electrode, may further comprise the steps:
(1) monocrystalline silicon piece is put into 60-90s in the aqueous solution of hydrofluoric acid and silver nitrate, the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4-8: 15-26 plates one deck silver nano-grain film with the method for electroless deposition;
(2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4-8: 15-26, corrosion temperature are 50-60 ℃, and etching time is 80-90min;
(3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 50-60 μ m, the centre is the thick silicon wafer of 100-120 μ m that does not have corrosion, grind off with the silicon nanowires of fine sandpaper the two sides, repeating step (1) and (2) after cleaning, until being corroded fully, the crucial phenomenon that the judgement silicon wafer is corroded into the silicon nanowire array film fully is: the silicon wafer that originally sinks to the corrosive liquid bottom is floating in solution;
(4) be silver-colored particle on the aqueous solution of nitric acid flush away silicon nanowires film of 10%-15% with volume ratio, with deionized water the silicon nanowires film cleaned up then;
(5) method with vacuum thermal evaporation plates the thick aluminium film of 200-300nm at the back side of silicon nanowires film, and annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 580-600 ℃, and the time is 1-2h, as the current collector of electrode; Perhaps wrap up the thick carbon aerogels of one deck 10-20 μ m on silicon nanowires film surface, vacuum-sintering then, sintering temperature is 650-700 ℃, and the time is 2-3h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
Advantage of the present invention and beneficial effect are:
(1) the invention provides a kind of method for preparing silicon nanowire array membrane electrode of easy and simple to handle, good reproducibility.
(2) utilize silicon nanowire array membrane electrode that the present invention prepares good performance to be arranged as the lithium ion battery of anode assembling, stable capacity reach present commercial use the graphitic carbon capacity 3-4 doubly.
(3) silicon nanowire array membrane electrode of the present invention's preparation has several advantages as the lithium ion battery anode: the first, and little silicon nanowires diameter can hold change in volume big in the battery charge and discharge process; The second, silicon-aluminum layer or carbon-coating have improved the electron-transporting of electrode; The 3rd, silicon nanowires has formed film, and electrode does not need binding agent and the conductive agent that can additionally gain in weight; The 4th, the preparation process of silicon nanowire array membrane electrode of the present invention is simple, and is cheap and be applicable to industrial production.
Description of drawings
Fig. 1 is the stereoscan photograph of the silicon nanowire array membrane electrode for preparing of the present invention, and wherein: (a) being the vertical view of untreated film, (b) is the vertical view of the back side film of aluminizing, and is the vertical view of the film of surface parcel carbon (c), (d) is the sectional view of film.
Fig. 2 is the chemical property curve of the back side that the present invention the prepares silicon nanowire array membrane electrode of aluminizing.
Fig. 3 is the chemical property curve of the silicon nanowire array membrane electrode of the surface parcel carbon for preparing of the present invention.
Embodiment
Embodiment one
The step of present embodiment is as follows:
(1) monocrystalline silicon piece is put into 60s in the aqueous solution of hydrofluoric acid and silver nitrate, the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4: 15, plate one deck silver nano-grain film with the method for electroless deposition;
(2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4: 15, corrosion temperature was 50 ℃, and etching time is 90min;
(3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 50 μ m, and the centre is the thick silicon wafer of 100 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully;
(4) be silver-colored particle on 10% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then;
(5) method with vacuum thermal evaporation plates the thick aluminium film of 300nm at the back side of silicon nanowires film; annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 600 ℃, and the time is 1h; as the current collector of electrode, promptly obtain silicon nanowire array membrane electrode.
The resulting silicon nanowire array membrane electrode test result of present embodiment is as follows: be full of in the glove box of argon gas assembling CR2032 button type lithium ion battery, with the silicon nanowires film electrode of working, metal lithium sheet is done electrode.Electrolyte is 1M LiPF
6Be dissolved in volume ratio and be in 1: 1 the EC and DMC solution.The lithium ion battery discharge capacity first time and charging capacity are respectively 3653mAh g
-1With 2409mAh g
-1Still kept about 1000mAh g after 30 circulations
-1Stable reversible capacity.
Embodiment two
The step of present embodiment is as follows:
(1) monocrystalline silicon piece is put into 80s in the aqueous solution of hydrofluoric acid and silver nitrate, the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 6: 20, plate one deck silver nano-grain film with the method for electroless deposition;
(2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 6: 20, corrosion temperature was 55 ℃, and etching time is 85min;
(3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 55 μ m, and the centre is the thick silicon wafer of 110 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully;
(4) be silver-colored particle on 12% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then;
(5) at the thick carbon aerogels of silicon nanowires film surface parcel one deck 10 μ m, vacuum-sintering then, sintering temperature is 700 ℃, and the time is 2h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
The resulting silicon nanowire array membrane electrode test result of present embodiment is as follows: be full of in the glove box of argon gas assembling CR2032 button type lithium ion battery, with the silicon nanowires film electrode of working, metal lithium sheet is done electrode.Electrolyte is 1M LiPF
6Be dissolved in volume ratio and be in 1: 1 the EC and DMC solution.Lithium ion battery discharges for the first time and charging capacity is respectively 3019mAhg
-1With 2566mAh g
-1, show that coulomb efficient is 85%.Still kept 1556mAh g after 30 circulations
-1Capacity.
Embodiment three
The step of present embodiment is as follows:
(1) monocrystalline silicon piece is put into 70s in the aqueous solution of hydrofluoric acid and silver nitrate, the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 8: 26, plate one deck silver nano-grain film with the method for electroless deposition;
(2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 8: 26, corrosion temperature was 60 ℃, and etching time is 80min;
(3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 60 μ m, and the centre is the thick silicon wafer of 120 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully;
(4) be silver-colored particle on 15% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then;
(5) method with vacuum thermal evaporation plates the thick aluminium film of 200nm at the back side of silicon nanowires film, and annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 580 ℃, and the time is 2h, as the current collector of electrode.Promptly obtain silicon nanowire array membrane electrode.
The resulting silicon nanowire array membrane electrode test result of present embodiment is as follows: be full of in the glove box of argon gas assembling CR2032 button type lithium ion battery, with the silicon nanowires film electrode of working, metal lithium sheet is done electrode.Electrolyte is 1M LiPF
6Be dissolved in volume ratio and be in 1: 1 the EC and DMC solution.The lithium ion battery discharge capacity first time and charging capacity are respectively 3656mAh g
-1With 2266mAh g
-1Still kept about 990mAh g after 25 circulations
-1Stable reversible capacity.
Embodiment four
The step of present embodiment is as follows:
(1) monocrystalline silicon piece is put into 60s in the aqueous solution of hydrofluoric acid and silver nitrate, the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4: 15, plate one deck silver nano-grain film with the method for electroless deposition;
(2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4: 15, corrosion temperature was 50 ℃, and etching time is 90min;
(3) after corrosion finished, two surfaces of silicon wafer all were that length is the silicon nanowire array of 50 μ m, and the centre is the thick silicon wafer of 100 μ m that does not corrode, and ground off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning;
(4) be silver-colored particle on 14% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then;
(5) at the thick carbon aerogels of silicon nanowires film surface parcel one deck 20 μ m, vacuum-sintering then, sintering temperature is 650 ℃, and the time is 3h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
The resulting silicon nanowire array membrane electrode test result of present embodiment is as follows: be full of in the glove box of argon gas assembling CR2032 button type lithium ion battery, with the silicon nanowires film electrode of working, metal lithium sheet is done electrode.Electrolyte is 1M LiPF
6Be dissolved in volume ratio and be in 1: 1 the EC and DMC solution.Lithium ion battery discharges for the first time and charging capacity is respectively 3344mAhg
-1With 2810mAh g
-1, show that coulomb efficient is 84%.Still kept 1326mAh g after 40 circulations
-1Capacity.
Claims (5)
1. the preparation method of silicon nanowire array membrane electrode is characterized in that, may further comprise the steps: (1) puts into monocrystalline silicon piece 60-90s in the aqueous solution of hydrofluoric acid and silver nitrate, and the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4-8: 15-26 plates one deck silver nano-grain film with the method for electroless deposition; (2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4-8: 15-26, corrosion temperature are 50-60 ℃, and etching time is 80-90min; (3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 50-60 μ m, the centre is the thick silicon wafer of 100-120 μ m that does not have corrosion, grind off with the silicon nanowires of fine sandpaper the two sides, repeating step (1) and (2) after cleaning, until being corroded fully, the crucial phenomenon that the judgement silicon wafer is corroded into the silicon nanowire array film fully is: the silicon wafer that originally sinks to the corrosive liquid bottom is floating in solution; (4) be silver-colored particle on the aqueous solution of nitric acid flush away silicon nanowires film of 10%-15% with volume ratio, with deionized water the silicon nanowires film cleaned up then; (5) method with vacuum thermal evaporation plates the thick aluminium film of 200-300nm at the back side of silicon nanowires film, and annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 580-600 ℃, and the time is 1-2h, as the current collector of electrode; Perhaps wrap up the thick carbon aerogels of one deck 10-20 μ m on silicon nanowires film surface, vacuum-sintering then, sintering temperature is 650-700 ℃, and the time is 2-3h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
2. preparation method according to claim 1 is characterized in that, may further comprise the steps: (1) puts into monocrystalline silicon piece 60s in the aqueous solution of hydrofluoric acid and silver nitrate, and the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4: 15, plate one deck silver nano-grain film with the method for electroless deposition; (2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4: 15, corrosion temperature was 50 ℃, and etching time is 90min; (3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 50 μ m, and the centre is the thick silicon wafer of 100 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully; (4) be silver-colored particle on 10% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then; (5) method with vacuum thermal evaporation plates the thick aluminium film of 300nm at the back side of silicon nanowires film; annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 600 ℃, and the time is 1h; as the current collector of electrode, promptly obtain silicon nanowire array membrane electrode.
3. preparation method according to claim 1 is characterized in that, may further comprise the steps: (1) puts into monocrystalline silicon piece 80s in the aqueous solution of hydrofluoric acid and silver nitrate, and the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 6: 20, plate one deck silver nano-grain film with the method for electroless deposition; (2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 6: 20, corrosion temperature was 55 ℃, and etching time is 85min; (3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 55 μ m, and the centre is the thick silicon wafer of 110 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully; (4) be silver-colored particle on 12% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then; (5) at the thick carbon aerogels of silicon nanowires film surface parcel one deck 10 μ m, vacuum-sintering then, sintering temperature is 700 ℃, and the time is 2h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
4. preparation method according to claim 1 is characterized in that, may further comprise the steps: (1) puts into monocrystalline silicon piece 70s in the aqueous solution of hydrofluoric acid and silver nitrate, and the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 8: 26, plate one deck silver nano-grain film with the method for electroless deposition; (2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 8: 26, corrosion temperature was 60 ℃, and etching time is 80min; (3) after corrosion finishes, two surfaces of silicon wafer all are that length is the silicon nanowire array of 60 μ m, and the centre is the thick silicon wafer of 120 μ m that does not corrode, and grinds off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning are until being corroded fully; (4) be silver-colored particle on 15% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then; (5) method with vacuum thermal evaporation plates the thick aluminium film of 200nm at the back side of silicon nanowires film, and annealing forms the Si-Al alloy under argon shield then, and annealing temperature is 580 ℃, and the time is 2h, as the current collector of electrode.Promptly obtain silicon nanowire array membrane electrode.
5. preparation method according to claim 1 is characterized in that, may further comprise the steps: (1) puts into monocrystalline silicon piece 60s in the aqueous solution of hydrofluoric acid and silver nitrate, and the volume ratio of each component is in the solution: HNO
3: HF: H
2O=1: 4: 15, plate one deck silver nano-grain film with the method for electroless deposition; (2) monocrystalline silicon piece that the surface is coated with the silver nano-grain film is put in the aqueous solution of hydrofluoric acid and hydrogen peroxide and is corroded, and the volume ratio of each component is in the solution: H
2O
2: HF: H
2O=1: 4: 15, corrosion temperature was 50 ℃, and etching time is 90min; (3) after corrosion finished, two surfaces of silicon wafer all were that length is the silicon nanowire array of 50 μ m, and the centre is the thick silicon wafer of 100 μ m that does not corrode, and ground off with the silicon nanowires of fine sandpaper with the two sides, repeating step (1) and (2) after cleaning; (4) be silver-colored particle on 14% the aqueous solution of nitric acid flush away silicon nanowires film with volume ratio, with deionized water the silicon nanowires film cleaned up then; (5) at the thick carbon aerogels of silicon nanowires film surface parcel one deck 20 μ m, vacuum-sintering then, sintering temperature is 650 ℃, and the time is 3h, and the carbon aerogels pyrolysis becomes carbon, as the current collector of electrode, promptly obtains silicon nanowire array membrane electrode.
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