CN102456926A - Novel three-dimensional lithium ion battery construction method - Google Patents
Novel three-dimensional lithium ion battery construction method Download PDFInfo
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- CN102456926A CN102456926A CN2010105232238A CN201010523223A CN102456926A CN 102456926 A CN102456926 A CN 102456926A CN 2010105232238 A CN2010105232238 A CN 2010105232238A CN 201010523223 A CN201010523223 A CN 201010523223A CN 102456926 A CN102456926 A CN 102456926A
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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 the field.
Background technology
Lithium ion battery has been widely used in receiving doting on of users deeply in the portable electronics such as mobile phone, notebook computer, and the electric automobile in future also has extraordinary application prospect, will produce deep effect to following people's life.The capacitance and the cycle performance of lithium ion battery constantly are improved, and capacity is bigger, quality is lighter, volume is littler, thickness lithium ion battery thinner, that price is lower constantly is pushed to the market.New electrode material and electrolyte are continually developed out, and they have, and capacity is big, price is low, non-environmental-pollution, advantage such as safe in utilization.Information age increases the demand to portable power source fast; Along with going deep into of Internet of Things research, the micro power that is embedded in some RF tags (RFID) is also very necessary.For power train in vehicle application, because slower battery charge speed and safety problem, electric automobile is also failed practicability at present.
The development of lithium ion battery mainly faces the challenge of two aspects, and the one, the assurance of fail safe; The 2nd, the raising of the performance of battery.Because the specific energy of battery is high, and electrolyte be organic combustibles etc. mostly, when battery heat generation speed during greater than radiating rate, just safety issue might occur.And improve the lithium ion battery performance, just must improve the charging rate and the energy density of lithium ion battery.Present approach comprises employing novel electrode material and adopts the novel battery structure.Taking the novel battery structure aspects, the research of three-dimensional structure is particularly important.Because it is under the situation that total current improves, current density does not improve, and therefore still compares safety; And if adopt the lithium ion battery of three-dimensional structure in the large scale system, under equal capacity, because its total current increases greatly, its charging interval can significantly 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 kinds of different modes is constituted 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) to carry out the research of 3-d microbatteries.The Israel scientist has also reported the three-dimensional lithium ion battery of making as framework with glass microchannel plate (MCP).In IEEE MEMS 2010 meetings of holding in Hong Kong that just finished, 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 basically based on dry etching; Like expensive equipment such as reactive ion etchings, or need complicated technology, 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 make up the novel three-dimensional lithium ion battery.
Summary of the invention
The objective of the invention is for a kind of preparation method of novel three-dimensional lithium ion battery is provided, to solve the problems referred to above of prior art.Technology is simple, production cost is low and can significantly improve the approach that lithium ion battery discharges and recharges speed and energy efficiency to explore one; And electrochemical etching prepared 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.
The object of the invention can be realized through following technical scheme.
A kind of preparation method of novel three-dimensional lithium ion battery, its concrete steps are following:
1) preparation of silicon microchannel plate: adopt electrochemical etching method,, obtain the complete silicon microchannel plate of rule in conjunction with the separation phenomenon certainly of silicon micro-channel in electrochemical etching.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 frozen machine, 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, earlier silicon micro-channel is carried out preprocessor.Utilize nickel salt solution under the effect of strong reductant, to make nickel be reduced to metallic nickel, obtain the nickel deposition layer at the surface and the sidewall of silicon micro-channel.The 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.This method is easy, and technical maturity is with low cost.Need to prove, in the manufacturing process of LiFePO4 subsequently, comprise this step of annealing, at this moment, metallic nickel also simultaneously with substrate silicon reaction formation nickel disilicide.
3) preparation of lithium iron phosphate positive material: adopt sol-gel method, with 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, drying repeatedly, on three-dimensional structure, obtain one deck and have certain thickness LiFePO4 gel.Pass through high-temperature heat treatment at last, obtain the LiFePO4 film, nickel metal layer in the above-mentioned steps and silicon microchannel plate reaction simultaneously generates the equally very low nickel disilicide of resistivity with the current collector as anode.This method is with low cost, and can reach the purpose of deposition covering preferably.
4) the electrolytical preparation of thin polymer film: adopt vacuum spin-coating method repeatedly, the three-dimensional high molecular polymer film of preparation one deck on the basis of the ready-made sample of step 3).The electrolyte thickness of this method preparation 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 CNT as solute, and be dissolved in deionized water.Above-mentioned sample and copper sheet are pieced together together, adopted traditional electrophoretic techniques, make and to fill up carbon nanometer tube negative pole material along the microchannel plate remaining space of the vertical direction of copper sheet.This 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 technology of battery: select the suitable electrolyte lithium salts, and it is dissolved in volatile solvent, utilize the sponginess of CNT, above-mentioned sample is immersed in the lithium salt solution, with the purpose of realization embedding lithium, and with its oven dry back assemble.This method has been avoided the dielectric film and the incompatible problem of subsequent preparation technology that possibly occur in the traditional preparation process electrolyte thin film method, and technology is simple, is easy to realize.
The concrete steps of step 1) are:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 8-12 Ω cm, and thickness is 200-400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
A) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried 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 steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
C) preparatory etching: the concentration that silicon chip is immersed in heating is 10-20min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place.
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used; Silicon chip is perpendicular in the electrochemical corrosion puts; Anode adopts the 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 the two poles of the earth solution respectively as electrode.In order to guarantee can to reach required current density in the etching, we have increased the 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
-2Carry out under current density and the 0.5-3.5KLux intensity of illumination, 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 enough satisfies the needs of three-dimensional lithium ion battery.
Step 2) concrete steps are: get the silicon micro-channel for preparing in the step 1),, then it was dipped in 1% the Triton X-100 aqueous solution about 30 seconds its thorough cleaning with deionized water, take out then; Composition in the plating bath 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.The pH value that adds ammoniacal liquor adjusting plating bath is heated to 60-90 ℃ to 8-9, and pretreated silicon microchannel plate is dipped in the nickel plating solution, realizes the parcel of nickel metal layer to silicon micro-channel through chemical deposition.
The concrete steps of step 3) are: the 1-3g citric acid is dissolved in the water, under agitation adds 6-8gFe (NO
3) 9H
21-2g LiOHH is dissolved in O and dissolving then successively
2O and 5-10g NH
4H
2PO4, after mixing, with the pH value of ammoniacal liquor regulator solution to 8.5-9.5,60～80 ℃ of following evaporating solvents in the water-bath.In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling.At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, go up nickel metal layer and pasc reaction generation nickel disilicide current collector in the step simultaneously the annealing of LiFePO4 dry film.
The concrete steps of step 4) are: with Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5-10g, acetone 20-50ml with magnetic stirrer to mixing, add 0.1-0.5g nanometer SiO again
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 the vacuum spin coating proceeding, and repeat the whirl coating process.At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
The concrete steps of step 5) are: the three-dimensional structure half-cell and the copper sheet that will prepare polymer dielectric are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
The concrete steps of step 6) are: adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, the 0.1-1g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution.Because the sponginess of CNT self, lithium hexafluoro phosphate also penetrates in the three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and the negative material.After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
The three-dimensional new type lithium ion battery that makes according to above technical scheme has following advantage:
1, adopt the specific area of the silicon microchannel plate that electrochemical etching obtains big, make the specific area of this novel three-dimensional lithium ion battery much larger than general conventional planar buckle type lithium-ion battery, charging and discharging currents is big, and energy density is high;
Although 2 charging and discharging currents are big, charging and discharging currents density does not increase, so the fail safe of three-dimensional new structure lithium ion battery is better; And under equal capacity, charging and discharging currents is big, and its charge-discharge velocity will improve than conventional planar battery greatly;
3, this battery production equipment and environmental requirement are not high, and production cost is lower.
Description of drawings
Fig. 1 is the three-dimensional iron phosphate lithium positive pole thin-film material of a Prepared by Sol Gel Method flow chart;
Fig. 2 is three-dimensional lithium ion battery structure generalized section.
Among the 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.
Its process chart is as shown in Figure 1.
The preparation of silicon microchannel plate:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 8 Ω cm, and thickness is 200 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
A) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 * 2 μ m apertures and pitch-row pattern, through steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
C) preparatory etching: the concentration that silicon chip is immersed in heating is 10min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place.
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used; Silicon chip is perpendicular in the electrochemical corrosion puts; Anode adopts the 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 the two poles of the earth solution respectively as electrode.In order to guarantee can to reach required current density in the etching, we have increased the 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
-2Carry out under current density and the 0.5KLux intensity of illumination, 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 enough satisfies the needs of three-dimensional lithium ion battery.
The preparation of nickel metal layer:
Get the silicon micro-channel for preparing, to its thorough cleaning, then it was dipped in 1% the Triton X-100 aqueous solution about 30 seconds, take out then with deionized water; Composition in the plating bath 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 and regulate the pH value to 8 of plating bath, be heated to 60 ℃, pretreated silicon microchannel plate is dipped in the nickel plating solution, realize the parcel of nickel metal layer silicon micro-channel through chemical deposition.
The preparation of lithium iron phosphate positive material:
The three-dimensional iron phosphate lithium positive pole thin-film material of Prepared by Sol Gel Method flow process is: the 1g citric acid is dissolved in the water, under agitation adds 6g Fe (NO
3) 9H
21g LiOHH is dissolved in O and dissolving then successively
2O and 5gNH
4H
2PO4, after mixing, using ammoniacal liquor to regulate the pH value is 8.5,60 ℃ of following evaporating solvents in the water-bath.In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling.At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, go up nickel metal layer and pasc reaction generation nickel disilicide current collector in the step simultaneously the annealing of LiFePO4 dry film.
The electrolytical preparation of thin polymer film:
With Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5g, acetone 20ml with magnetic stirrer to mixing, add 0.1g nanometer SiO again
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 the vacuum spin coating proceeding, and repeat the whirl coating process.At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
The preparation of carbon nanometer tube negative pole material:
Three-dimensional structure half-cell that prepares polymer dielectric and copper sheet are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
The embedding lithium technology of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, the 0.1g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution.Because the sponginess of CNT self, lithium hexafluoro phosphate also penetrates in the three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and the negative material.After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
The three-dimensional lithium ion battery structure section for preparing is as shown in Figure 2.
Embodiment 2
The preparation of silicon microchannel plate:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 12 Ω cm, and thickness is 400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
A) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 * 2 μ m apertures and pitch-row pattern, through steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
C) preparatory etching: the concentration that silicon chip is immersed in heating is 20min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place.
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used; Silicon chip is perpendicular in the electrochemical corrosion puts; Anode adopts the 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 the two poles of the earth solution respectively as electrode.In order to guarantee can to reach required current density in the etching, we have increased the 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
-2Carry out under current density and the 3.5KLux intensity of illumination, 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 enough satisfies the needs of three-dimensional lithium ion battery.
The preparation of nickel metal layer:
Get the silicon micro-channel for preparing, to its thorough cleaning, then it was dipped in 1% the Triton X-100 aqueous solution about 30 seconds, take out then with deionized water; Composition in the plating bath 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 and regulate the pH value to 9 of plating bath, be heated to 90 ℃, pretreated silicon microchannel plate is dipped in the nickel plating solution, realize the parcel of nickel metal layer silicon micro-channel through chemical deposition.
The preparation of lithium iron phosphate positive material:
The three-dimensional iron phosphate lithium positive pole thin-film material of Prepared by Sol Gel Method flow process is: the 3g citric acid is dissolved in the water, under agitation adds 8g Fe (NO
3) 9H
22g LiOHH is dissolved in O and dissolving then successively
2O and 10g NH
4H
2PO4, after mixing, using ammoniacal liquor to regulate the pH value is 9.5,80 ℃ of following evaporating solvents in the water-bath.In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling.At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, go up nickel metal layer and pasc reaction generation nickel disilicide current collector in the step simultaneously the annealing of LiFePO4 dry film.
The electrolytical preparation of thin polymer film:
With Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 10g, acetone 50ml with magnetic stirrer to mixing, add 0.5g nanometer SiO again
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 the vacuum spin coating proceeding, and repeat the whirl coating process.At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
The preparation of carbon nanometer tube negative pole material:
Three-dimensional structure half-cell that prepares polymer dielectric and copper sheet are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
The embedding lithium technology of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, the 1g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution.Because the sponginess of CNT self, lithium hexafluoro phosphate also penetrates in the three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and the negative material.After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
Embodiment 3
The preparation of silicon microchannel plate:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 10 Ω cm, and thickness is 300 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
A) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 3 * 3 μ m apertures and pitch-row pattern, through steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
C) preparatory etching: the concentration that silicon chip is immersed in heating is 15min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place.
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used; Silicon chip is perpendicular in the electrochemical corrosion puts; Anode adopts the 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 the two poles of the earth solution respectively as electrode.In order to guarantee can to reach required current density in the etching, we have increased the 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
-2Carry out under current density and the 2KLux intensity of illumination, 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 enough satisfies the needs of three-dimensional lithium ion battery.
The preparation of nickel metal layer:
Get the silicon micro-channel for preparing, to its thorough cleaning, then it was dipped in 1% the Triton X-100 aqueous solution about 30 seconds, take out then with deionized water; Composition in the plating bath 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 and regulate the pH value to 9 of plating bath, be heated to 70 ℃, pretreated silicon microchannel plate is dipped in the nickel plating solution, realize the parcel of nickel metal layer silicon micro-channel through chemical deposition.
The preparation of lithium iron phosphate positive material:
The three-dimensional iron phosphate lithium positive pole thin-film material of Prepared by Sol Gel Method flow process is: the 2g citric acid is dissolved in the water, under agitation adds 7g Fe (NO
3) 9H
22g LiOHH is dissolved in O and dissolving then successively
2O and 7gNH
4H
2PO4, after mixing, using ammoniacal liquor to regulate the pH value is 8.5,70 ℃ of following evaporating solvents in the water-bath.In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling.At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, go up nickel metal layer and pasc reaction generation nickel disilicide current collector in the step simultaneously the annealing of LiFePO4 dry film.
The electrolytical preparation of thin polymer film:
With Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 8g, acetone 40ml with magnetic stirrer to mixing, add 0.3g nanometer SiO again
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 the vacuum spin coating proceeding, and repeat the whirl coating process.At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
The preparation of carbon nanometer tube negative pole material:
Three-dimensional structure half-cell that prepares polymer dielectric and copper sheet are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
The embedding lithium technology of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, the 0.5g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution.Because the sponginess of CNT self, lithium hexafluoro phosphate also penetrates in the three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and the negative material.After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
Embodiment 4
The preparation of silicon microchannel plate:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 9 Ω cm, and thickness is 250 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
A) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried oxygen, oxidated layer thickness is 1000 dusts.
B) photoetching: adopt the mask plate of 2 * 2 μ m apertures and pitch-row pattern, through steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
C) preparatory etching: the concentration that silicon chip is immersed in heating is 17min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place.
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used; Silicon chip is perpendicular in the electrochemical corrosion puts; Anode adopts the 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 the two poles of the earth solution respectively as electrode.In order to guarantee can to reach required current density in the etching, we have increased the 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
-2Carry out under current density and the 2.5KLux intensity of illumination, 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 enough satisfies the needs of three-dimensional lithium ion battery.
The preparation of nickel metal layer:
Get the silicon micro-channel for preparing, to its thorough cleaning, then it was dipped in 1% the Triton X-100 aqueous solution about 30 seconds, take out then with deionized water; Composition in the plating bath 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 and regulate the pH value to 8 of plating bath, be heated to 80 ℃, pretreated silicon microchannel plate is dipped in the nickel plating solution, realize the parcel of nickel metal layer silicon micro-channel through chemical deposition.
The preparation of lithium iron phosphate positive material:
The three-dimensional iron phosphate lithium positive pole thin-film material of Prepared by Sol Gel Method flow process is: the 1g citric acid is dissolved in the water, under agitation adds 8g Fe (NO
3) 9H
22g LiOHH is dissolved in O and dissolving then successively
2O and 5-10g NH
4H
2PO4, after mixing, using ammoniacal liquor to regulate the pH value is 8.5,65 ℃ of following evaporating solvents in the water-bath.In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding. rotating speed 4000r/min, even glue time 30s.Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling.At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, go up nickel metal layer and pasc reaction generation nickel disilicide current collector in the step simultaneously the annealing of LiFePO4 dry film.
The electrolytical preparation of thin polymer film:
With Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 6g, acetone 30ml with magnetic stirrer to mixing, add 0.2g nanometer SiO again
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 the vacuum spin coating proceeding, and repeat the whirl coating process.At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
The preparation of carbon nanometer tube negative pole material:
Three-dimensional structure half-cell that prepares polymer dielectric and copper sheet are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
The embedding lithium technology of battery:
Adopt lithium hexafluoro phosphate (LiPF
6) as electrolyte lithium salt.In the anhydrous glove box of vacuum, the 0.3g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution.Because the sponginess of CNT self, lithium hexafluoro phosphate also penetrates in the three-dimensional structure as electrolyte lithium salt, in final embedded polymer thing electrolytic thin-membrane and the negative material.After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
Claims (7)
1. the preparation method of a novel three-dimensional lithium ion battery, its concrete steps are following:
1) preparation of silicon microchannel plate: adopt electrochemical etching method,, obtain the complete silicon microchannel plate of rule in conjunction with the separation phenomenon certainly of silicon micro-channel in electrochemical etching;
2) preparation of nickel metal layer: adopt electroless plating method, earlier silicon micro-channel is carried out preprocessor; Utilize nickel salt solution under the effect of strong reductant, to make nickel be reduced to metallic nickel, obtain the nickel deposition layer at the surface and the sidewall of silicon micro-channel;
3) preparation of lithium iron phosphate positive material: adopt sol-gel method, with 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, drying repeatedly, on three-dimensional structure, obtain one deck and have certain thickness LiFePO4 gel; Pass through high-temperature heat treatment again, obtain the LiFePO4 film, simultaneously step 2) in the equally very low nickel disilicide of nickel metal layer and silicon microchannel plate reaction generation resistivity with current collector as anode;
4) the electrolytical preparation of thin polymer film: adopt vacuum spin-coating method repeatedly, the three-dimensional high molecular polymer film of preparation one deck on the basis of the ready-made sample of step 3);
5) preparation of carbon nanometer tube negative pole material: select water miscible CNT as solute; And be dissolved in deionized water; Step 4) sample and copper sheet are pieced together together; Adopt traditional electrophoretic techniques, make and 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 technology of battery: select the suitable electrolyte lithium salts, and it is dissolved in volatile solvent, utilize the sponginess of CNT, the step 5) sample is immersed in the lithium salt solution, and with its oven dry back assemble.
2. the preparation method of novel three-dimensional lithium ion battery according to claim 1 is characterized in that: the concrete steps of step 1) are:
A) select for use the monocrystalline silicon piece that uses on the commercial production to be P type < 100>crystal orientation, resistivity is 8-12 Ω cm, and thickness is 200-400 μ m;
B) adopt the Radio Corporation of America (RCA) standard cleaning technology that silicon chip is cleaned;
C) oxidation of silicon substrate, photoetching, preparatory etching;
D) oxidation: the standard thermal oxidation technology, adopt dried oxygen-wet oxygen-dried oxygen, oxidated layer thickness is 1000 dusts;
E) photoetching: adopt the mask plate of 2 * 2 μ m or 3 * 3 μ m apertures and pitch-row pattern, through steps such as standard linging, gluing, preceding baking, exposure, development, back baking, wet etching silicon dioxide layers, to leave the square hole pattern in surface of silicon.
F) preparatory etching: the concentration that silicon chip is immersed in heating is 10-20min in 50% TMAH (TMAH) aqueous solution, to form pit at the window place;
D) electrochemical etching of silicon substrate: etching tank adopts hydrofluoric acid reaction vessel material polytetrafluoroethylene (Teflon) commonly used, and silicon chip is perpendicular in the electrochemical corrosion puts, and anode adopts the 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 the two poles of the earth solution respectively as electrode, and be provided with the back lighting system, it is 0-12V that light source adopts voltage range; Rated power is the direct current Halogen lamp LED of 100w, and electrochemical etching is at 15-20mAcm
-2Carry out under current density and the 0.5-3.5KLux intensity of illumination, the thickness of the silicon microchannel plate of gained generally can be controlled in tens microns to 200 microns.
3. the preparation method of novel three-dimensional lithium ion battery according to claim 1; It is characterized in that: step 2) concrete steps be: get the silicon micro-channel for preparing in the step 1); With deionized water to its thorough cleaning; Then it is dipped in 20-30 second in 1% the Triton X-100 aqueous solution, takes out then; Composition in the plating bath 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, deionized water 50ml; The pH value that adds ammoniacal liquor adjusting plating bath is heated to 60-90 ℃ to 8-9, and pretreated silicon microchannel plate is dipped in the nickel plating solution, realizes the parcel of nickel metal layer to silicon micro-channel through chemical deposition.
4. the preparation method of novel three-dimensional lithium ion battery according to claim 1 is characterized in that: the concrete steps of step 3) are: the 1-3g citric acid is dissolved in the water, under agitation adds 6-8gFe (NO
3) 9H
21-2g LiOHH is dissolved in O and dissolving then successively
2O and 5-10g NH
4H
2PO4, after mixing, with the pH value of ammoniacal liquor regulator solution to 8.5-9.5,60～80 ℃ of following evaporating solvents in the water-bath; In the solvent evaporation process, form colloidal sol gradually, on KW-4A type sol evenning machine, adopt the vacuum spin coating proceeding, rotating speed 4000r/min, even glue time 30s; Then that the LiFePO4 wet film is dry in drying box, taking-up repeats the technical process of front after treating its cooling; At last, under 700 ℃ of high temperature,, obtain the LiFePO4 film, simultaneously step 2 to the annealing of LiFePO4 dry film) in nickel metal layer and pasc reaction generation nickel disilicide current collector.
5. the preparation method of novel three-dimensional lithium ion battery according to claim 1; It is characterized in that: the concrete steps of step 4) are: with Kynoar-hexafluoropropylene copolymer (PVDF-HFP) 5-10g, acetone 20-50ml with magnetic stirrer to mixing, add 0.1-0.5g nanometer SiO again
2Or Al
2O
3Powder continues to stir, and is cooled to room temperature, obtains transparent high viscosity liquid, and is same, on KW-4A type sol evenning machine, adopts the vacuum spin coating proceeding, and repeats the whirl coating process; At last, surface and the sidewall in three-dimensional structure obtains the layer of even polymer electrolyte film.
6. the preparation method of novel three-dimensional lithium ion battery according to claim 1 is characterized in that: the concrete steps of step 5) are: the three-dimensional structure half-cell and the copper sheet that will prepare polymer dielectric are pieced together together, as work electrode; To the electrodes use platinum electrode; Water-soluble carbon nanometer tube is dissolved in the deionized water, fully stirring and dissolving; Immerse in the solution with work electrode with to electrode again, add offset on two electrodes and press; Finally, along the vertical direction of copper sheet, at the whole deposition of carbon nanotubes of the remaining space inside of microchannel, as the negative material of battery.
7. the preparation method of novel three-dimensional lithium ion battery according to claim 1; It is characterized in that: the concrete steps of step 6) are: adopt lithium hexafluoro phosphate as electrolyte lithium salt; In the anhydrous glove box of vacuum; The 0.1-1g lithium hexafluoro phosphate fully is dissolved in the 20ml acetone, the battery sample for preparing carbon nanometer tube negative pole material with electrophoresis is immersed in 5min in the above-mentioned solution; After taking out sample,, and in glove box, it is assembled into button cell with its 60 ℃ of oven dry 24 hours under vacuum condition.
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| CN1655381A (en) * | 2005-03-09 | 2005-08-17 | 武汉理工大学 | A total solid state lithium micro cell positive electrode film and method for making same |
| JP2007508671A (en) * | 2003-10-14 | 2007-04-05 | コミサリア、ア、レネルジ、アトミク | A small battery in which at least one electrode and an electrolyte each contain a common atomic group [XY1Y2Y3Y4], and a method for manufacturing the small battery |
| CN101030655A (en) * | 2007-04-04 | 2007-09-05 | 天津大学 | Micro-battery structure and its production |
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| JP2007508671A (en) * | 2003-10-14 | 2007-04-05 | コミサリア、ア、レネルジ、アトミク | A small battery in which at least one electrode and an electrolyte each contain a common atomic group [XY1Y2Y3Y4], and a method for manufacturing the small battery |
| CN1655381A (en) * | 2005-03-09 | 2005-08-17 | 武汉理工大学 | A total solid state lithium micro cell positive electrode film and method for making same |
| CN101030655A (en) * | 2007-04-04 | 2007-09-05 | 天津大学 | Micro-battery structure and its production |
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| CN104900849A (en) * | 2015-07-02 | 2015-09-09 | 中国科学院电子学研究所 | Method for forming porous structure on surface of three-dimensional column array |
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