CN1901256A - Lithium ion cell negative pole and its producing method - Google Patents
Lithium ion cell negative pole and its producing method Download PDFInfo
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- CN1901256A CN1901256A CNA2006100110401A CN200610011040A CN1901256A CN 1901256 A CN1901256 A CN 1901256A CN A2006100110401 A CNA2006100110401 A CN A2006100110401A CN 200610011040 A CN200610011040 A CN 200610011040A CN 1901256 A CN1901256 A CN 1901256A
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Abstract
This invention relates to the negative of a Li ionic battery and a preparing method, in which, the electrode is prepared by metal oxide as the active material with the shape of nm lines or tubes and assembled directly on the battery collector, SnO is taken as the negative material of the battery, a nm porous film as a template to prepare the metal oxide to a beam arrayed nm line with a sol-gel method to be assembled on the collector to form the negative of the battery, and the diameter of the nm line is 50-200nm.
Description
Technical field: the present invention relates to a kind of lithium ion battery negative and preparation method thereof, adopt nanoscale lines or nanotube-shaped metal oxide materials, belong to the lithium ion battery material technical field as the negative electrode active material of lithium ion battery.
Background technology: compare with lead-acid battery, nickel-cadmium cell, Ni-MH battery, lithium ion battery is owing to have high operating voltage, specific energy density, memory-less effect and eco-friendly advantage, since putting goods on the market, developed rapidly nineteen ninety, occupied the market mainstream at present, become notebook computer, the main power supply of mobile communications tool and camera.Because the miniaturization of electronic product requires lithium ion battery to have higher energy density.In recent years, for the strategic concerns of the soaring and new energy development of oil price, the research and development of electric automobile start climax once more, and lithium-ion-power cell is rapidly developed as the power supply of electric automobile.The negative material of lithium ion battery is graphite-like material with carbon element or petroleum coke product at present---middle carbon phase microballoon, the reversible removal lithium embedded of such material functional, but the capacity of material is on the low side, especially repid discharge ability wretched insufficiency as power battery cathode the time.
Can be used for the material that lithium ion battery negative discharges and recharges, metal and Li electrochemistry alloyings such as Al, Sn, Si, Sb, lithium ion is shifted to negative pole and metal formation alloy Li from positive pole during charging
xM, lithium is deviate from during discharge, and the lithium storage content of generation is far longer than graphite type material, such as tin alloying Li
4.4The theoretical capacity of Sn is 992mAh/g, and alloying with silicon Li
4.4The theoretical capacity of Si is up to 4191mAh/g.But this type of material produces very big volumetric expansion and contraction in the removal lithium embedded process, and this serious bulk effect can cause the breakage of material to come off, and the circulation volume of battery is descended fast.
In order to improve the cycle performance of these metal materials, the normal means that adopt are metal alloyizations of electro-chemical activity metal and electrochemistry inertia.For example the researcher adopts Sn and Cu, Sb, Ag, Ni etc. element alloyed, improved cycle performance to a certain extent, but it is undesirable to produce effects.Fuji Photo Film Co., Ltd. has prepared combined oxidation objects system Sn in nineteen ninety-five
xSi
yP
zMO, the oxide of using the non-electrochemical activity supports and has disperseed the particle of several nanometer tin-oxides as network skeleton, stops it to grow up in the electrochemistry circulation, has therefore improved the cycle performance of material greatly.Also adopted mechanical alloying method, chemical precipitation method, solid-phase sintering to get composite oxides method and sputter coating method etc. in the research of report, above preparation method disperses embedding cloth to improve circulation ability in inert component in order to obtain fine tin particles.But the cycle performance of such material is still waiting further raising at present.Because tin particles disperses embedding cloth in inert component in metal alloy method and composite oxides method, lithium ion must could arrive tin through the diffusion in the solid dielectric, makes battery fast charging and discharging scarce capacity.
Summary of the invention: the objective of the invention is to overcome the deficiency of prior art, a kind of lithium ion battery negative and preparation method thereof is provided,, improve the specific capacity and the fast charging and discharging ability of battery by changing the form of the reactive metal material that battery cathode uses.
Technical scheme of the present invention is: this lithium ion battery negative active matter is a metal oxide, has nano wire (or nanotube-shaped) profile form, directly is assembled on the battery collector electrode; This electrode metal active material can be tin oxide, and the diameter of its nano wire or nanotube is 50～200nm.
The preparation method of this lithium ion battery negative, be as the battery cathode active material with metal oxide, adopt nano-porous film as template, (diameter is 50nm～200nm) for nano wire of the preparation of metal oxides fasciculation being arranged with sol-gel process or nanotube, directly be assembled on the collector electrode, form battery cathode.The porous membrane template is nanoporous oxidation film or polymer film, and metal oxide is a tin oxide, and the concrete preparation process of battery cathode comprises: at first with the inorganic salts that contain tin or organotin as raw material (as stannic chloride SnCl
2.5H
2O is a raw material), be dissolved in water or the alcohol, obtain tin concentration and be 3～10 moles contain solution of tin (as tin chloride solution); Added the additive ageing then 24～72 hours, obtaining viscosity is the colloidal sol of 2～4 centipoises (cp); The oxidation film or the thin polymer film that will have the cylinder hole that is arranged in parallel are used as the surface that template is placed on collector electrode metal, inject the good colloidal sol of ageing on film, stop to make colloidal sol diffuse into the film hole and gel in hole in 1～2 hour; Under 25～150 ℃, associate again dry 24 hours (atmosphere without limits, oxidizing atmosphere is better), remove the solvent composition, obtained the tin oxide of crystallization then 350～650 ℃ of calcinings in 15～90 minutes; In alkali lye, soak 10～30 minutes (as aqueous solution such as NaOH, KOH) at last, with the electrode that obtains after oxide or the polymer film removal forming by parallel pencil nano wire or nanotube.Also available deionized water soaks flush away alkali lye, with electrode vacuumize, fully removes moisture.
The inorganic salts that contain tin among the present invention can be that the chloride of tin is (as stannic chloride SnCl
2.5H
2The mixture of one or several O) or in the STANNOUS SULPHATE CRYSTALLINE, nitric acid tin; Organotin is unrestricted, can adopt ethanol tin, butanols tin, one or several in the isopropyl alcohol tin etc.Pure unrestricted as solvent can be adopted ethanol or butanols; Used additive is hydrochloric acid or nitric acid when making solvent with alcohol, and addition is 1%～5% of a tin molar concentration; Used additive is an ammoniacal liquor when using water as solvent, and addition is identical with the molal quantity of tin.The digestion time of colloidal sol mainly in order to control the colloidal sol viscosity at 2～4 centipoises (cp), made colloidal sol enter hole effectively between 24 hours to 72 hours.
Metal oxide active material of the present invention is a tin oxide, used template can be apertured polymeric film (as the Merlon nucleopore membranes), perhaps porous oxide film is (as anodic alumina films, has the cylinder hole that is arranged in parallel, hole ratio height), the nano-pore aperture on the template and the diameter of nano wire correspond to 50nm～200nm, the thickness of film can be determined according to actual needs, general corresponding with the length of the nano wire that is obtained, thickness can select between 5～100um that (nanowire length is big more, thickness is big more), guarantee the normal shaping of nano wire, the removal that helps film gets final product.Because anodised aluminium has the cylinder hole that is arranged in parallel, hole ratio height can bear higher heating-up temperature, adopts porous oxide film as template, can guarantee the formation of cell negative electrode material pencil nano wire.
More than the electrode of Huo Deing can be used as the negative pole and the anodal rechargeable battery that is assembled into into 3.5V voltage of lithium ion battery, and positive pole can adopt LiCoO2, LiNiO2, LiMn2O4.
The present invention is owing to be prepared into parallel pencil nano wire with electrode active material, and directly is assembled in preparation process on the collector electrode and (is similar to the mane on the brush), forms battery cathode and be directly used in to be assembled into battery.In such electrode structure, electrolyte contacts with the surface of nano wire, has increased response area; And do not contact between the nano wire, metal active material (as Sn) or its alloy can have enough space frees to expand when discharging and recharging, eliminate effectively that volumetric expansion causes damage effect.Simultaneously, this open structure provides bigger electrode/electrolyte response area, and Li only carries out short-range diffusion in metal Sn base solid-state material, and electrode can be worked under big charge-discharge velocity.Therefore, electrode of the present invention have response area big, when discharging and recharging the free wxpansion space big, adapt to advantage such as various environment of big charge-discharge velocity, can make battery have high cycle performance, high battery specific capacity and fast charging and discharging ability.
Description of drawings:
Fig. 1 is the stereoscan photograph of the tin oxide nano tube bundle side of employing the present invention preparation;
Fig. 2 is the stereoscan photograph in the tin oxide nano tube bundle front of employing the present invention preparation;
Fig. 3 is the constituent analysis of the tin oxide nano tube of employing the present invention preparation;
Fig. 4 is the cycle performance of assembled battery of the present invention under the 1C multiplying power.
Embodiment: technology contents of the present invention is described further below in conjunction with drawings and Examples.
Embodiment 1: this lithium ion battery negative adopts tin oxide to make, and has nanotube-shaped profile form, directly is assembled on the battery collector electrode, and the overall diameter of its nanotube is 100nm.
The preparation of this lithium ion battery negative is with stannic chloride (SnCl
2.5H
2O) be raw material, be dissolved in the ethanol, obtain tin concentration and be 5 moles the solution of tin that contains; The hydrochloric acid that adds tin concentration 5% obtained colloidal sol in 24 hours through ageing, and colloidal sol has viscosity 3.2 centipoises (cp); The anodic aluminum oxide film that will have the cylinder hole that is arranged in parallel is used as the surface that template is placed on collector electrode metal copper, as template anodised aluminium thickness 40um, and aperture 100nm; On film, inject the good colloidal sol of ageing, stop and made colloidal sol diffuse into the film hole in 1 hour and in hole, solidify; Removed the solvent composition in 24 hours 90 ℃ of dryings; Obtained the tin-oxide of crystallization in 30 minutes through 440 ℃ of calcinings; In NaOH alkali lye, soak 30 minutes with the electrode that obtains after the aluminium oxide removal forming by parallel pencil nanotube; Soak 30 minutes flush away alkali lye with deionized water, electrode was fully removed moisture in 24 hours 100 ℃ of vacuumizes.
Adopt this negative pole directly to assemble lithium ion battery, adopt button cell 2032 to make test battery.Electrode slice is cut to the disk of diameter 13mm, and electrolyte is 1: 1 PC: DMC, and electrolyte is the LiPF6 of 1M, and the how empty film of polypropylene is made barrier film, the lithium disk that adopts diameter 13mm thickness 0.1mm as test battery to electrode.Battery is assemblied in the glove box of strict control moisture and operates.Battery loop test voltage at 0.1V between the 1.3V.
The circulation volume of this battery and cycle performance are seen shown in the figure four.
Embodiment 2: this lithium ion battery negative adopts tin oxide to make, and has nanotube-shaped profile form, directly is assembled on the battery collector electrode, and the overall diameter of its nanotube is 200nm.
The preparation of this lithium ion battery negative is with stannic chloride (SnCl
4.2H
2O) be raw material, be dissolved in the water, obtain tin concentration and be 5 moles the solution of tin that contains; Add the ammoniacal liquor with the identical molal quantity of tin, through ageing acquisition in 72 hours colloidal sol, colloidal sol has viscosity 2.2 centipoises (cp); The anodic aluminum oxide film that will have the cylinder hole that is arranged in parallel is used as the surface that template is placed on the collector electrode metal platinized platinum, as template anodised aluminium thickness 50um, and aperture 200nm; On film, inject the good colloidal sol of ageing, stop and made colloidal sol diffuse into the film hole and gel in hole in 1 hour; Removed the solvent composition in 24 hours 120 ℃ of dryings; Obtained the tin-oxide of crystallization in 30 minutes through 550 ℃ of calcinings; In NaOH alkali lye, soak 30 minutes with the electrode that obtains after the aluminium oxide removal forming by parallel pencil nanotube.Soak 30 minutes flush away alkali lye with deionized water, electrode was fully removed moisture in 24 hours 100 ℃ of vacuumizes.
Adopt this negative pole directly to assemble lithium ion battery, adopt button cell 2032 to make test battery.Electrode slice is cut to the disk of diameter 13mm, and electrolyte is 1: 1 PC: DMC, and electrolyte is the LiPF6 of 1M, and the how empty film of polypropylene is made barrier film, the lithium disk that adopts diameter 13mm thickness 0.1mm as test battery to electrode.Battery is assemblied in the glove box of strict control moisture and operates.Battery loop test voltage at 0.1V between the 1.3V.
This battery discharge capacity of the tenth time under the 2C electric current is 483mAh/g, and the 30 time discharge capacity is 485mAh/g, and the 50 time discharge capacity is 430mAh/g, and cycle performance is good.
Embodiment 3: this lithium ion battery negative adopts tin oxide to make, and has nano wire profile form, directly is assembled on the battery collector electrode, and the diameter of its nano wire is 50nm.
The preparation of this lithium ion battery negative is with STANNOUS SULPHATE CRYSTALLINE (SnSO
4) be raw material, be dissolved in the water, obtain tin concentration and be 3 moles the solution of tin that contains; Add the ammoniacal liquor additive identical with the molar concentration of tin; Obtained colloidal sol in 36 hours through ageing, colloidal sol has viscosity 2 centipoises (cp); Polycarbonate membrane is used as the surface that template is placed on collector electrode metal copper, as template Merlon thickness 5um, aperture 50nm; On film, inject the good colloidal sol of ageing, stop and made colloidal sol diffuse into the film hole in 2 hours and in hole, solidify; Removed the solvent composition in 24 hours 125 ℃ of dryings, the tin oxide through 350 ℃ of calcinings acquisition in 15 minutes crystallization soaked 10 minutes in NaOH alkali lye then, sloughed polymer template.Soak 30 minutes flush away alkali lye with deionized water, electrode was fully removed moisture in 24 hours 100 ℃ of vacuumizes.
Adopt this negative pole directly to assemble lithium ion battery, adopt button cell 2032 to make test battery.Electrode slice is cut to the disk of diameter 13mm, and electrolyte is 1: 1 PC: DMC, and electrolyte is the LiPF6 of 1M, and polypropylene porous film is made barrier film, the lithium disk that adopts diameter 13mm thickness 0.1mm as test battery to electrode.Battery is assemblied in the glove box of strict control moisture and operates.Battery loop test voltage at 0.1V between the 1.3V.
This battery secondary discharge capacity under the 2C electric current is 650mAh/g, and the 30 time discharge capacity is 580mAh/g, and the 50 time discharge capacity is 530mAh/g, and cycle performance is better.
Embodiment 4: this lithium ion battery negative adopts tin oxide to make, and has nano wire profile form, directly is loaded on the battery collector electrode, and the diameter of its nano wire is 120nm.
The preparation of this lithium ion battery negative is to be raw material with ethanol tin, is dissolved in the butanols, obtains tin concentration and be 10 moles the solution of tin that contains; The nitric acid that adds tin concentration 1% is through the colloidal sol of ageing in 48 hours acquisition viscosity 4 centipoises (cp); The multiaperture pellumina (thickness 100um, aperture 120nm) that will have the cylinder hole that is arranged in parallel is placed on the surface of collector electrode metal copper as template; On film, inject the good colloidal sol of ageing, stop and made colloidal sol diffuse into the film hole in 1.5 hours and in hole, solidify; Removed the solvent composition in 24 hours 25 ℃ of dryings; Obtained the tin-oxide of crystallization in 90 minutes through 650 ℃ of calcinings; In KOH alkali lye, soak 20 minutes with the electrode that obtains after the pellumina removal becoming by parallel pencil set of nanowires; Soak 30 minutes flush away alkali lye with deionized water, electrode was fully removed moisture in 24 hours 100 ℃ of vacuumizes.
Adopt this negative pole directly to assemble lithium ion battery, adopt button cell 2032 to make test battery.Electrode slice is cut to the disk of diameter 13mm, and electrolyte is 1: 1 PC: DMC, and electrolyte is the LiPF6 of 1M, and the how empty film of polypropylene is made barrier film, the lithium disk that adopts diameter 13mm thickness 0.1mm as test battery to electrode.Battery is assemblied in the glove box of strict control moisture and operates.Battery loop test voltage at 0.1V between the 1.3V.
This battery secondary discharge capacity under the 1C electric current is 627mAh/g, and the 30 time discharge capacity is 421mAh/g, and cycle performance is better.
Embodiment 5: this lithium ion battery negative adopts tin oxide to make, and has nanotube-shaped profile form, directly is assembled on the battery collector electrode, and the overall diameter of its nanotube is 100nm.
The preparation of this lithium ion battery negative is with stannic chloride SnCl
2.5H
2O) and STANNOUS SULPHATE CRYSTALLINE be raw material, be dissolved in the water, obtain tin concentration and be 8 moles the solution of tin that contains; Add the ammoniacal liquor additive identical with the molar concentration of tin; Obtained colloidal sol in 72 hours through ageing, colloidal sol has viscosity 3 centipoises (cp); The anodic aluminum oxide film that will have the cylinder hole that is arranged in parallel is used as the surface that template is placed on the collector electrode metal platinized platinum, as template anodised aluminium thickness 30um, and aperture 100m; On film, inject the good colloidal sol of ageing, stop and made colloidal sol diffuse into the film hole and gel in hole in 2 hours; Removed the solvent composition in 24 hours 150 ℃ of dryings; Obtained the tin oxide of crystallization in 30 minutes through 440 ℃ of calcinings; In NaOH alkali lye, soak 10 minutes with the electrode that obtains after the aluminium oxide removal forming by parallel pencil nanotube.Soak 30 minutes flush away alkali lye with deionized water, electrode was fully removed moisture in 24 hours 100 ℃ of vacuumizes.
Adopt this negative pole directly to assemble lithium ion battery, adopt button cell 2032 to make test battery.Electrode slice is cut to the disk of diameter 13mm, and electrolyte is 1: 1 PC: DMC, and electrolyte is the LiPF6 of 1M, and the how empty film of polypropylene is made barrier film, the lithium disk that adopts diameter 13mm thickness 0.1mm as test battery to electrode.Battery is assemblied in the glove box of strict control moisture and operates.Battery loop test voltage at 0.1V between the 1.3V.
This battery secondary discharge capacity under the 1C electric current is 580Ah/g, and the 30 time discharge capacity is 432mAh/g, and cycle performance is better.
Claims (7)
1. a lithium ion battery negative adopts metal oxide to make electrode active material, it is characterized in that this electro-chemical activity metal oxide has nano wire or nanotube profile form, directly is assembled on the battery collector electrode.
2. lithium ion battery negative according to claim 1, the diameter that it is characterized in that described nano wire or nanotube is 50～200nm.
3. lithium ion battery negative according to claim 1 and 2 is characterized in that described electrode material is a tin oxide.
4. the preparation method of the described lithium ion battery negative of claim 1, with metal oxide as the battery cathode active material, it is characterized in that adopting the nanoporous template, the nano wire or the nanotube that cooperate sol-gel process that the preparation of metal oxides fasciculation is arranged, directly be assembled on the collector electrode, form battery cathode.
5. the preparation method of lithium ion battery negative according to claim 4 is characterized in that foraminous die plate is multiaperture pellumina or polymer film, and metal oxide is a tin oxide, and the concrete preparation process of battery cathode comprises:
5.1, be dissolved in water or the alcohol as raw material with the inorganic salts that contain tin or organotin, obtain tin concentration and be 3～10 moles the solution of tin that contains;
5.2 add additive and ageing 24～72 hours, obtaining viscosity is the colloidal sol of 2～4 centipoises;
Be placed on the surface of collector electrode metal 5.3 will have the oxidation film of the cylinder hole that is arranged in parallel or thin polymer film as template, on film, inject the good colloidal sol of ageing then, stop and made colloidal sol diffuse into the film hole and gel in hole in 1～2 hour;
5.4 under 25～150 ℃, carried out drying 24 hours, remove the solvent composition, obtained the tin oxide of crystallization then in 15～90 minutes 350～650 ℃ of calcinings;
5.5 in alkali lye, soaked 10～30 minutes, with the electrode that obtains after oxidation film or the polymer film removal forming by parallel pencil nano wire or nanotube.
6, according to the preparation method of claim 4 or 5 described lithium ion battery negatives, when it is characterized in that making solvent, add hydrochloric acid or nitric acid additive with alcohol, addition is 1%～5% of a tin concentration; When using water as solvent, add the ammoniacal liquor additive, addition is identical with the molal quantity of tin.
7. according to the preparation method of claim 4 or 5 described lithium ion battery negatives, it is characterized in that the aperture of nano wire and nanoporous template corresponds to 50nm～200nm.
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| CNA2006100110401A CN1901256A (en) | 2006-07-13 | 2006-07-13 | Lithium ion cell negative pole and its producing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012019492A1 (en) * | 2010-08-13 | 2012-02-16 | 上海中科深江电动车辆有限公司 | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof |
| CN103219490A (en) * | 2012-01-23 | 2013-07-24 | 通用汽车环球科技运作有限责任公司 | Fade-resistant high capacity electrodes for a lithium-ion battery |
-
2006
- 2006-07-13 CN CNA2006100110401A patent/CN1901256A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012019492A1 (en) * | 2010-08-13 | 2012-02-16 | 上海中科深江电动车辆有限公司 | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof |
| US9985273B2 (en) | 2010-08-13 | 2018-05-29 | Shanghai Zhongke Shenjiang Electric Vehicle Co., Ltd | Three-dimensional nanosized porous metal oxide electrode material of lithium ion battery and preparation method thereof |
| CN103219490A (en) * | 2012-01-23 | 2013-07-24 | 通用汽车环球科技运作有限责任公司 | Fade-resistant high capacity electrodes for a lithium-ion battery |
| CN103219490B (en) * | 2012-01-23 | 2016-12-28 | 通用汽车环球科技运作有限责任公司 | Fade-resistant high capacity electrodes for lithium ion battery |
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