CN102456926B - Novel three-dimensional lithium ion battery construction method - Google Patents
Novel three-dimensional lithium ion battery construction method Download PDFInfo
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Abstract
The invention discloses a construction method of a lithium ion battery, and particularly relates to a preparation method of a novel three-dimensional lithium ion battery. Belongs to the field of microelectronic process. The preparation method comprises the following steps: 1. preparing a silicon microchannel plate, 2 preparing a nickel metal layer, 3 preparing a lithium iron phosphate anode material, 4 preparing a polymer film electrolyte, 5 preparing a carbon nano tube cathode material, and 6 embedding lithium in a battery. The invention has the advantages that: the silicon microchannel plate obtained by adopting electrochemical etching has large specific surface area, so that the specific surface area of the novel three-dimensional lithium ion battery is far larger than that of the common traditional plane button lithium ion battery, the charging and discharging current is large, and the energy density is high; the safety of the lithium ion battery with the three-dimensional novel structure is better; under the same capacity, the charge-discharge current is large, and the charge-discharge rate is greatly improved compared with that of the traditional planar battery; the battery has low requirements on production equipment and environment and low production cost.
Description
Technical field
The present invention relates to a kind of construction method of lithium ion battery, be specially a kind of preparation method of novel three-dimensional lithium ion battery.Belong to microelectronic technique and make field.
Background technology
Lithium ion battery has been widely used in, in the portable electronics such as mobile phone, notebook computer, being deeply subject to doting on of users, also has extraordinary application prospect at following electric automobile, will produce deep effect to following people's life.Capacitance and the cycle performance of lithium ion battery are constantly improved, and capacity is larger, quality lithium ion battery lighter, that volume is less, thickness is thinner, price is lower is constantly pushed to the market.New electrode material and electrolyte are continually developed out, the advantages such as they have, and capacity is large, price is low, non-environmental-pollution, use safety.Information age makes the demand rapid growth to portable power source; Along with going deep into of Internet of Things research, be embedded in micro power in some radio-frequency (RF) tag (RFID) also very necessary.For power train in vehicle application, due to slower battery charging rate and safety problem, electric automobile is also failed practical at present.
The development of lithium ion battery mainly faces the challenge of two aspects, and the one, the guarantee of fail safe; The 2nd, the raising of the performance of battery.Because the specific energy of battery is high, and electrolyte is mostly organic combustibles etc., in the time that battery heat generation speed is greater than radiating rate, just likely occurs safety issue.And raising performance of lithium ion battery, just necessary charging rate and the energy density that improves lithium ion battery.Current approach comprises employing new electrode materials and adopts novel battery structure.Taking novel battery structure aspects, the research of three-dimensional structure is particularly important.Because it is in the situation that total current improves, current density does not improve, therefore still safer; And if adopt the lithium ion battery of three-dimensional structure in large scale system, under equal capacity, because its total current increases greatly, its charging interval can greatly reduce.For power train in vehicle application, if can use such three-dimensional structure lithium ion battery, its benefit that brings people is self-evident.As far back as 2003, people just imagined the mutual 3-d microbatteries structure of arranging of columnar electrode, and the three-dimensional batteries that the both positive and negative polarity of arranging by several different modes is formed has carried out emulation.Next year, under the support of research institute of USN, California, USA university has carried out and utilizes C-MEMS (graphite MEMS (micro electro mechanical system)) to carry out the research of 3-d microbatteries.Israel scientist has also reported the three-dimensional lithium ion battery of making using glass microchannel plate (MCP) as framework.Just finished in the IEEE of Held in Hong Kong MEMS 2010 meetings, the B.Dunn of California, USA university has also done the invitation report about 3-d microbatteries.
But, with the structure of the upper class's three-dimensional structure substantially based on dry etching, as expensive equipment such as reactive ion etchings, or need complicated technique, and the depth-to-width ratio of gained microchannel is not high, this has just seriously limited the cost of manufacture of lithium ion battery, and has limited the specific area of three-dimensional structure.Therefore, developing low-cost, the three-dimensional structure of high-aspect-ratio is extremely urgent to build novel three-dimensional lithium ion battery.
Summary of the invention
The object of the invention is the preparation method for a kind of novel three-dimensional lithium ion battery is provided, to solve the problems referred to above of prior art.Explore one technique be simple, production cost is low and can significantly improve lithium ion battery the approach that discharges and recharges speed and energy efficiency, and electrochemical etching is prepared to the method for silicon micro-channel and the preparation method of lithium ion battery combines, work out a kind of framework of novel three-dimensional lithium ion battery.
Object of the present invention can be achieved through the following technical solutions.
A preparation method for novel three-dimensional lithium ion battery, its concrete steps are as follows:
1) preparation of silicon microchannel plate: adopt electrochemical etching method, the self-separation phenomenon in conjunction with silicon micro-channel in electrochemical etching, obtains the silicon microchannel plate that rule is complete.Experimental provision is the horizontal etching device of the Teflon plastic production of independent research, specifically sees patent ZL2004 1 0099139.2, and other also have circulating refrigerator, Halogen lamp LED group and LabVIEW light auxiliary etch program, and reagent is common reagent.
2) preparation of nickel metal layer: adopt electroless plating method, first silicon micro-channel is carried out to preprocessor.Utilize nickel salt solution to make nickel be reduced to metallic nickel under the effect of strong reductant, obtain nickel sedimentary deposit at surface and the sidewall of silicon micro-channel.Chemical nickel-plating plating solution composition comprises: six hydration nickel sulfate 5-10g, ammonium sulfate 1-3g, ammonium fluoride 10-12g, 0.1% Triton X-100 aqueous solution 1ml, lauryl sodium sulfate 0.3-1g, natrium citricum 3-6g, deionized water 50ml.The method is easy, and technical maturity is with low cost.It should be noted that, comprise this step of annealing in the manufacturing process of LiFePO4 subsequently, now, metallic nickel also simultaneously and substrate silicon reaction formation nickel disilicide.
3) preparation of lithium iron phosphate positive material: adopt sol-gel method, by 1-3g citric acid, 6-8gFe (NO
3) 9H
2o, 1-2g LiOHH
2o, 5-10g NH
4h
2pO4 mixing, heating, evaporation obtain LiFePO4 colloidal sol.Through gluing, whirl coating, vacuum suction, dry repeatedly, in three-dimensional structure, obtain one deck and there is certain thickness LiFePO4 gel.Finally by crossing high-temperature heat treatment, obtain LiFePO4 film, the nickel metal layer in above-mentioned steps generates the same very low nickel disilicide of resistivity using the current collector as anode with silicon microchannel plate reaction simultaneously.The method is with low cost, and can reach good deposition covering object.
4) preparation of polymer film electrolyte: adopt vacuum spin-coating method repeatedly, in step 3) prepare the three-dimensional high molecular polymer film of one deck on the basis of ready-made sample.Electrolyte thickness prepared by the method is thin, good uniformity, and pick up is high, and ionic conductivity is good, and ionic mobility is high.
5) preparation of carbon nanometer tube negative pole material: select water miscible carbon nano-tube as solute, and be dissolved in deionized water.Together with above-mentioned sample is pieced together with copper sheet, adopt traditional electrophoretic techniques, make to fill up carbon nanometer tube negative pole material along the microchannel plate remaining space of the vertical direction of copper sheet.The method can successfully realize the optimization of silicon microchannel plate inner space utilance, and improves electrode material thickness, thereby improves battery performance.
6) the embedding lithium technique of battery: select suitable electrolyte lithium salt, and be dissolved in volatile solvent, utilize the sponginess of carbon nano-tube, above-mentioned sample is immersed in lithium salt solution, to realize the object of embedding lithium, and assembling battery after being dried.The problem that the dielectric film that this method has been avoided tradition to prepare may occurring in electrolyte thin film method and follow-up preparation technology are incompatible, and technique is simple, is easy to realization.
Step 1) concrete steps be:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 8-12 Ω cm, and thickness is 200-400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 × 2 μ m or 3 × 3 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after the step such as baking, wet etching silicon dioxide layer, to output square hole pattern in surface of silicon.
C) pre-etching: silicon chip is immersed in to 10-20min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place.
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, and platinum guaze is put into respectively to the two poles of the earth solution as electrode.In order to ensure can to reach required current density in etching, we have increased back lighting system, and light source adopts the direct current Halogen lamp LED of Ou Silang company (OSRAM), voltage range 0-12V, rated power 100w.Electrochemical etching is at 15-20mAcm
-2under current density and 0.5-3.5KLux intensity of illumination, carry out, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns, and its depth-to-width ratio is the needs of capable of meeting requirements on three-dimensional lithium ion battery enough.
Step 2) concrete steps be: get step 1) in the silicon micro-channel for preparing, it is thoroughly cleaned with deionized water, be then dipped in 1% the Triton X-100 aqueous solution about 30 seconds, then take out; Composition in the plating solution of electroless-plating nickel is nickelous sulfate 5-10g, ammonium fluoride 10-12g, ammonium sulfate 1-3g, lauryl sodium sulfate 0.3-1g, natrium citricum 3-6g, deionized water 50ml.Add ammoniacal liquor to regulate the pH value of plating solution to 8-9, be heated to 60-90 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition.
Step 3) concrete steps be: 1-3g citric acid is dissolved in the water, under agitation adds 6-8gFe (NO
3) 9H
2o also dissolves, and then dissolves in successively 1-2g LiOHH
2o and 5-10g NH
4h
2pO4, after being uniformly mixed, by the pH value of ammoniacal liquor regulator solution to 8.5-9.5, evaporating solvent at 60～80 DEG C in water-bath.In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above.Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously the nickel metal layer in previous step and pasc reaction generation nickel disilicide current collector.
Step 4) concrete steps be: Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5-10g, acetone 20-50ml magnetic stirrer, to mixing, then are added to 0.1-0.5g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid.Equally, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, and repeat whirl coating process.Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
Step 5) concrete steps be: together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
Step 6) concrete steps be: adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, 0.1-1g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material.Due to the sponginess of carbon nano-tube self, lithium hexafluoro phosphate also penetrates in three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and negative material.Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
The three-dimensional new type lithium ion battery making according to above technical scheme has advantages of following:
The specific area of the silicon microchannel plate that 1, employing electrochemical etching obtains is large, makes the specific area of this novel three-dimensional lithium ion battery much larger than general conventional planar fastening lithium ionic cell, and charging and discharging currents is large, and energy density is high;
Although 2 charging and discharging currents are large, charging and discharging currents density does not increase, therefore the fail safe of three-dimensional new structure lithium ion battery is better; And under equal capacity, charging and discharging currents is large, and its charge-discharge velocity will improve greatly than conventional planar battery;
3, this battery production equipment and environmental requirement are not high, and production cost is lower.
Brief description of the drawings
Fig. 1 is that sol-gal process is prepared three-dimensional iron phosphate lithium positive pole thin-film material flow chart;
Fig. 2 is three-dimensional lithium ion battery structural profile schematic diagram.
In figure: 1, silicon substrate 2, carbon nanometer tube negative pole 3, iron phosphate lithium positive pole 4, nickel dioxide current collector 5, polymer dielectric.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
Embodiment 1
Its process chart as shown in Figure 1.
The preparation of silicon microchannel plate:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 8 Ω cm, and thickness is 200 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 × 2 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after the step such as baking, wet etching silicon dioxide layer, to output square hole pattern in surface of silicon.
C) pre-etching: silicon chip is immersed in to 10min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place.
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, and platinum guaze is put into respectively to the two poles of the earth solution as electrode.In order to ensure can to reach required current density in etching, we have increased back lighting system, and light source adopts the direct current Halogen lamp LED of Ou Silang company (OSRAM), voltage range 0-12V, rated power 100w.Electrochemical etching is at 15mAcm
-2under current density and 0.5KLux intensity of illumination, carry out, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns, and its depth-to-width ratio is the needs of capable of meeting requirements on three-dimensional lithium ion battery enough.
The preparation of nickel metal layer:
Get the silicon micro-channel preparing, it is thoroughly cleaned with deionized water, be then dipped in 1% the Triton X-100 aqueous solution about 30 seconds, then take out; Composition in the plating solution of electroless-plating nickel is six hydration nickel sulfate 5g, ammonium sulfate 1g, ammonium fluoride 10g, 0.1% Triton X-100 aqueous solution 1ml, lauryl sodium sulfate 0.3g, natrium citricum 3g, deionized water 50ml.Add ammoniacal liquor to regulate the pH value to 8 of plating solution, be heated to 60 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition.
The preparation of lithium iron phosphate positive material:
Sol-gal process is prepared three-dimensional iron phosphate lithium positive pole thin-film material flow process: 1g citric acid is dissolved in the water, under agitation adds 6g Fe (NO
3) 9H
2o also dissolves, and then dissolves in successively 1g LiOHH
2o and 5gNH
4h
2pO4, after being uniformly mixed, regulating pH value with ammoniacal liquor is 8.5, evaporating solvent at 60 DEG C in water-bath.In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above.Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously the nickel metal layer in previous step and pasc reaction generation nickel disilicide current collector.
The preparation of polymer film electrolyte:
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5g, acetone 20ml by magnetic stirrer to mixing, then add 0.1g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid.Equally, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, and repeat whirl coating process.Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
The preparation of carbon nanometer tube negative pole material:
Together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
The embedding lithium technique of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, 0.1g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material.Due to the sponginess of carbon nano-tube self, lithium hexafluoro phosphate also penetrates in three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and negative material.Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
The three-dimensional lithium ion battery structural profile preparing as shown in Figure 2.
Embodiment 2
The preparation of silicon microchannel plate:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 12 Ω cm, and thickness is 400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 × 2 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after the step such as baking, wet etching silicon dioxide layer, to output square hole pattern in surface of silicon.
C) pre-etching: silicon chip is immersed in to 20min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place.
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, and platinum guaze is put into respectively to the two poles of the earth solution as electrode.In order to ensure can to reach required current density in etching, we have increased back lighting system, and light source adopts the direct current Halogen lamp LED of Ou Silang company (OSRAM), voltage range 0-12V, rated power 100w.Electrochemical etching is at 20mAcm
-2under current density and 3.5KLux intensity of illumination, carry out, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns, and its depth-to-width ratio is the needs of capable of meeting requirements on three-dimensional lithium ion battery enough.
The preparation of nickel metal layer:
Get the silicon micro-channel preparing, it is thoroughly cleaned with deionized water, be then dipped in 1% the Triton X-100 aqueous solution about 30 seconds, then take out; Composition in the plating solution of electroless-plating nickel is six hydration nickel sulfate 10g, ammonium sulfate 3g, ammonium fluoride 12g, 0.1% Triton X-100 aqueous solution 1ml, lauryl sodium sulfate 1g, natrium citricum 6g, deionized water 50ml.Add ammoniacal liquor to regulate the pH value to 9 of plating solution, be heated to 90 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition.
The preparation of lithium iron phosphate positive material:
Sol-gal process is prepared three-dimensional iron phosphate lithium positive pole thin-film material flow process: 3g citric acid is dissolved in the water, under agitation adds 8g Fe (NO
3) 9H
2o also dissolves, and then dissolves in successively 2g LiOHH
2o and 10g NH
4h
2pO4, after being uniformly mixed, regulating pH value with ammoniacal liquor is 9.5, evaporating solvent at 80 DEG C in water-bath.In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above.Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously the nickel metal layer in previous step and pasc reaction generation nickel disilicide current collector.
The preparation of polymer film electrolyte:
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 10g, acetone 50ml by magnetic stirrer to mixing, then add 0.5g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid.Equally, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, and repeat whirl coating process.Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
The preparation of carbon nanometer tube negative pole material:
Together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
The embedding lithium technique of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, 1g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material.Due to the sponginess of carbon nano-tube self, lithium hexafluoro phosphate also penetrates in three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and negative material.Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
Embodiment 3
The preparation of silicon microchannel plate:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 10 Ω cm, and thickness is 300 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 3 × 3 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after the step such as baking, wet etching silicon dioxide layer, to output square hole pattern in surface of silicon.
C) pre-etching: silicon chip is immersed in to 15min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place.
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, and platinum guaze is put into respectively to the two poles of the earth solution as electrode.In order to ensure can to reach required current density in etching, we have increased back lighting system, and light source adopts the direct current Halogen lamp LED of Ou Silang company (OSRAM), voltage range 0-12V, rated power 100w.Electrochemical etching is at 15mAcm
-2under current density and 2KLux intensity of illumination, carry out, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns, and its depth-to-width ratio is the needs of capable of meeting requirements on three-dimensional lithium ion battery enough.
The preparation of nickel metal layer:
Get the silicon micro-channel preparing, it is thoroughly cleaned with deionized water, be then dipped in 1% the Triton X-100 aqueous solution about 30 seconds, then take out; Composition in the plating solution of electroless-plating nickel is six hydration nickel sulfate 6g, ammonium sulfate 2g, ammonium fluoride 11g, 0.1% Triton X-100 aqueous solution 1ml, lauryl sodium sulfate 0.5g, natrium citricum 5g, deionized water 50ml.Add ammoniacal liquor to regulate the pH value to 9 of plating solution, be heated to 70 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition.
The preparation of lithium iron phosphate positive material:
Sol-gal process is prepared three-dimensional iron phosphate lithium positive pole thin-film material flow process: 2g citric acid is dissolved in the water, under agitation adds 7g Fe (NO
3) 9H
2o also dissolves, and then dissolves in successively 2g LiOHH
2o and 7gNH
4h
2pO4, after being uniformly mixed, regulating pH value with ammoniacal liquor is 8.5, evaporating solvent at 70 DEG C in water-bath.In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above.Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously the nickel metal layer in previous step and pasc reaction generation nickel disilicide current collector.
The preparation of polymer film electrolyte:
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 8g, acetone 40ml by magnetic stirrer to mixing, then add 0.3g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid.Equally, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, and repeat whirl coating process.Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
The preparation of carbon nanometer tube negative pole material:
Together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
The embedding lithium technique of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, 0.5g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material.Due to the sponginess of carbon nano-tube self, lithium hexafluoro phosphate also penetrates in three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and negative material.Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
Embodiment 4
The preparation of silicon microchannel plate:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 9 Ω cm, and thickness is 250 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 × 2 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after the step such as baking, wet etching silicon dioxide layer, to output square hole pattern in surface of silicon.
C) pre-etching: silicon chip is immersed in to 17min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place.
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, and platinum guaze is put into respectively to the two poles of the earth solution as electrode.In order to ensure can to reach required current density in etching, we have increased back lighting system, and light source adopts the direct current Halogen lamp LED of Ou Silang company (OSRAM), voltage range 0-12V, rated power 100w.Electrochemical etching is at 16mAcm
-2under current density and 2.5KLux intensity of illumination, carry out, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns, and its depth-to-width ratio is the needs of capable of meeting requirements on three-dimensional lithium ion battery enough.
The preparation of nickel metal layer:
Get the silicon micro-channel preparing, it is thoroughly cleaned with deionized water, be then dipped in 1% the Triton X-100 aqueous solution about 30 seconds, then take out; Composition in the plating solution of electroless-plating nickel is six hydration nickel sulfate 6g, ammonium sulfate 2g, ammonium fluoride 10g, 0.1% Triton X-100 aqueous solution 1ml, lauryl sodium sulfate 0.4g, natrium citricum 4g, deionized water 50ml.Add ammoniacal liquor to regulate the pH value to 8 of plating solution, be heated to 80 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition.
The preparation of lithium iron phosphate positive material:
Sol-gal process is prepared three-dimensional iron phosphate lithium positive pole thin-film material flow process: 1g citric acid is dissolved in the water, under agitation adds 8g Fe (NO
3) 9H
2o also dissolves, and then dissolves in successively 2g LiOHH
2o and 5-10g NH
4h
2pO4, after being uniformly mixed, regulating pH value with ammoniacal liquor is 8.5, evaporating solvent at 65 DEG C in water-bath.In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above.Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously the nickel metal layer in previous step and pasc reaction generation nickel disilicide current collector.
The preparation of polymer film electrolyte:
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 6g, acetone 30ml by magnetic stirrer to mixing, then add 0.2g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid.Equally, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, and repeat whirl coating process.Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
The preparation of carbon nanometer tube negative pole material:
Together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
The embedding lithium technique of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, 0.3g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material.Due to the sponginess of carbon nano-tube self, lithium hexafluoro phosphate also penetrates in three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and negative material.Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
Claims (3)
1. a preparation method for three-dimensional lithium ion battery, its concrete steps are as follows:
1) preparation of silicon microchannel plate: adopt electrochemical etching method, the self-separation phenomenon in conjunction with silicon micro-channel in electrochemical etching, obtains the silicon microchannel plate that rule is complete;
2) preparation of nickel metal layer: first silicon micro-channel is carried out to preprocessor; Utilize nickel salt solution to make nickel be reduced to metallic nickel under the effect of strong reductant, obtain nickel sedimentary deposit at surface and the sidewall of silicon micro-channel;
3) preparation of lithium iron phosphate positive material: adopt sol-gel method, by 1-3g citric acid, 6-8gFe (NO
3)
39H
2o, 1-2g LiOHH
2o and 5-10g NH
4h
2pO
4mixing, heating, evaporation obtain LiFePO4 colloidal sol; Through gluing, whirl coating, vacuum suction, dry repeatedly, in three-dimensional structure, obtain one deck and there is certain thickness LiFePO4 gel; Pass through again high-temperature heat treatment, obtain LiFePO4 film, simultaneously step 2) in nickel metal layer with the same very low nickel disilicide of silicon microchannel plate reaction generation resistivity using the current collector as anode;
4) preparation of polymer film electrolyte: adopt vacuum spin-coating method repeatedly, in step 3) prepare the three-dimensional high molecular polymer film of one deck on the basis of ready-made sample;
5) preparation of carbon nanometer tube negative pole material: select water miscible carbon nano-tube as solute, and be dissolved in deionized water, by step 4) together with sample pieces together with copper sheet, adopt traditional electrophoretic techniques, make to fill up carbon nanometer tube negative pole material along the microchannel plate remaining space of the vertical direction of copper sheet;
6) the embedding lithium technique of battery: select suitable electrolyte lithium salt, and be dissolved in volatile solvent, utilize the sponginess of carbon nano-tube, by step 5) sample immerses in lithium salt solution, and assembling battery after being dried;
Step 1) concrete steps be:
A) selecting the monocrystalline silicon piece using in industrial production is P type <100> crystal orientation, and resistivity is 8-12 Ω
cm, thickness is 200-400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technique to clean silicon chip;
C) oxidation of silicon substrate, photoetching, pre-etching;
A) oxidation: standard thermal oxidation technology, adopt dry oxygen-wet oxygen-dry oxygen, oxidated layer thickness is 1000 dusts;
B) photoetching: adopt the mask plate of 2 × 2 μ m or 3 × 3 μ m apertures and pitch-row pattern, through standard linging, gluing, front baking, exposure, development, after dry, wet etching silicon dioxide layer step, to output square hole pattern in surface of silicon;
C) pre-etching: silicon chip is immersed in to 10-20min in Tetramethylammonium hydroxide (TMAH) aqueous solution that the concentration of heating is 50%, to form pit at window place;
D) electrochemical etching of silicon substrate: etching tank adopts the conventional reaction vessel material polytetrafluoroethylene (Teflon) of hydrofluoric acid, in electrochemical corrosion, silicon chip is perpendicular puts, anode adopts conducting solution saturated nacl aqueous solution to contact with the silicon back side, negative electrode is the hydrofluoric acid solution of 2M, platinum guaze is put into respectively to the two poles of the earth solution as electrode, and be provided with back lighting system, light source adopts voltage range for being less than or equal to 12V, rated power is the direct current Halogen lamp LED of 100w, and electrochemical etching is at 15-20mAcm
-2under current density and 0.5-3.5KLux intensity of illumination, carry out, the THICKNESS CONTROL of the silicon microchannel plate of gained is at tens microns to 200 microns;
Step 2) concrete steps be: get step 1) in the silicon micro-channel for preparing, it is thoroughly cleaned with deionized water, be then dipped in 20-30 second in 1% the Triton X-100 aqueous solution, then take out; Composition in the plating solution of electroless-plating nickel is six hydration nickel sulfate 5-10g, ammonium fluoride 10-12g, ammonium sulfate 1-3g, lauryl sodium sulfate 0.3-1g, natrium citricum 3-6g and deionized water 50ml; Add ammoniacal liquor to regulate the pH value of plating solution to 8-9, be heated to 60-90 DEG C, pretreated silicon microchannel plate is dipped in nickel plating solution, realize the parcel of nickel metal layer to silicon micro-channel by chemical deposition;
Step 3) concrete steps be: 1-3g citric acid is dissolved in the water, under agitation adds 6-8gFe (NO
3)
39H
2o also dissolves, and then dissolves in successively 1-2g LiOHH
2o and 5-10g NH
4h
2pO
4, after being uniformly mixed, by the pH value of ammoniacal liquor regulator solution to 8.5-9.5, evaporating solvent at 60～80 DEG C in water-bath; In solvent evaporation process, form gradually colloidal sol, on KW-4A type sol evenning machine, adopt vacuum spin coating proceeding, rotating speed 4000r/min, even glue time 30s; Then LiFePO4 wet film is dry in drying box, take out after it is cooling, repeat technical process above; Finally, at 700 DEG C of high temperature, to the annealing of LiFePO4 dry film, obtain LiFePO4 film, simultaneously step 2) in nickel metal layer and pasc reaction generation nickel disilicide current collector;
Step 4) concrete steps be: Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5-10g, acetone 20-50ml magnetic stirrer, to mixing, then are added to 0.1-0.5g nanometer SiO
2or Al
2o
3powder, continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid, same, adopts vacuum spin coating proceeding, and repeat whirl coating process on KW-4A type sol evenning machine; Finally, obtain the uniform polymer electrolyte film of one deck at surface and the sidewall of three-dimensional structure.
2. the preparation method of three-dimensional lithium ion battery according to claim 1, is characterized in that: step 5) concrete steps be: together with the three-dimensional structure half-cell that prepares polymer dielectric is pieced together with copper sheet, as work electrode; Electrode is adopted to platinum electrode; Water-soluble carbon nanometer tube is dissolved in deionized water, fully stirring and dissolving; Immerse in solution by work electrode with to electrode again, on two electrodes, add offset and press; Finally, along the vertical direction of copper sheet, the whole deposition of carbon nanotubes of remaining space inside in microchannel, as the negative material of battery.
3. the preparation method of three-dimensional lithium ion battery according to claim 1, it is characterized in that: step 6) concrete steps be: adopt lithium hexafluoro phosphate as electrolyte lithium salt, in the anhydrous glove box of vacuum, 0.1-1g lithium hexafluoro phosphate is fully dissolved in 20ml acetone, will be immersed in 5min in above-mentioned solution with the battery sample that electrophoresis prepares carbon nanometer tube negative pole material; Take out after sample, by its under vacuum condition 60 DEG C dry 24 hours, and in glove box, be assembled into button cell.
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