CN100391033C - Lithium-ion film cell negative pole and preparing method - Google Patents
Lithium-ion film cell negative pole and preparing method Download PDFInfo
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- CN100391033C CN100391033C CNB2005100409279A CN200510040927A CN100391033C CN 100391033 C CN100391033 C CN 100391033C CN B2005100409279 A CNB2005100409279 A CN B2005100409279A CN 200510040927 A CN200510040927 A CN 200510040927A CN 100391033 C CN100391033 C CN 100391033C
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- film
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The method includes steps: mixing lithium acetate and cobalt acetate according to 0.25-4:1 mol ratio, and solving the admixture to carbitol to form solution of precursor body in density of metal positive ion as 0.001-0.02 mol/liter; solution flowed to spray head in 2-4 ml./hr uniform speed, adjusting interval between spray head and substrate as 1-4 cm, controlling constant temperature 200-300 deg.C for substrate, adjusting DC voltage between spray head and substrate to obtain steady and even spray; obtaining XLi2O .YcoO film of composite oxides in thickness 1-200 micro; film is in 3D mesh structure, and mesh size as 2-30 micro, Li2O and CoO as amorphous phase and crystallite state respectively; 2 theta of characteristic peak of X ray for incidence to copper target as 36, 42.5, 61.5, 74 degrees, and relative intensity ratio of peak as 1:1-1.7 for 2 theta being as 42.5 and 36 degrees. Features are: high first discharge capacity, low first capacity loss and excellent cycle performance.
Description
Technical field
The invention belongs to preparation method's technical field of miniature lithium ion battery membrane electrode, particularly adopt electrostatic spray sedimentation (ESD) preparation to consist of the composite oxides miniature lithium ion battery negative film of cobalt oxide and lithia.
Background technology
In recent years, along with mobile phone, the appearance of products such as notebook computer, volume is little, and the lithium ion battery that energy density is high moves towards commercialization gradually, and becomes the focus of research.Therefore, the preparation high-performance, the microelectronic component of the electrode pair of film lithium ion battery exploitation cheaply has important meaning.
International monopoly International Patent WO01/31720A1 has introduced and has adopted the method for chemical vapour deposition (CVD) or sputter to prepare the negative material of silicon alloy film as lithium ion battery, but because alloy electrode volume in charge and discharge process has bigger pucker ﹠ bloat, can cause active material to come off, the cycle performance of battery is reduced from substrate; The used membrane equipment of this method costs an arm and a leg in addition, and operating condition requires harsh.
Holland " solid-state ionics " (Solid State Ionics; 170 (2004) 105-109) propose to use pulsed laser deposition (PLD) preparation cobaltic-cobaltous oxide negative pole film; this method processing step is loaded down with trivial details; need under oxygen atmosphere protection, operation just can obtain cobaltosic oxide, and the cobaltosic oxide reduction becomes cobalt oxide and makes capacitance loss bigger after discharge first.
Holland's " energy " magazine (Journal of power sources, 97-98 (2001) 282-286) has been introduced and has been used the electrostatic spray precipitation equipment to prepare the positive pole material of lithium cobalt acid of lithium-ion film cell.But up to the present, do not see that use electrostatic spray sedimentation prepares miniature lithium ion battery negative material XLi
2The report of OYCoO membrane electrode.
Summary of the invention:
The present invention proposes a kind of XLi of consisting of
2OYCoO (X: Y=0.125-2: lithium-ion film cell negative pole 1) and preparation method thereof, to overcome the above-mentioned defective of prior art.
Lithium-ion film cell negative pole of the present invention is characterised in that it is the XLi of thickness 1-200 micron
2OYCoO composite oxide film, wherein X: Y=0.125-2: 1; Film is a tridimensional network, and the size of mesh is the 2-30 micron; Li wherein
2The structure of O and CoO is respectively amorphous state and crystallite attitude; 2 θ of the X ray characteristic peak that the incident of copper target produces are 36 °, 42.5 °, 61.5 ° and 74 °, and its 2 θ is that the peak relative intensity ratio of 42.5 ° and 36 ° is 1: 1-1.7.
The preparation method of lithium-ion film cell negative pole of the present invention, it is characterized in that lithium acetate: cobalt acetate is pressed 0.25-4: 1 mixed in molar ratio, be dissolved in carbitol (butyl carbito1) solvent, forming metal cation concentration is the precursor solution of 0.001-0.02 mol, with this solution with 2-4 milliliter/hour at the uniform velocity flow to fog-spray nozzle, the adjusting fog-spray nozzle is 1-4 centimetre to the distance of substrate, control heated substrate constant temperature is at 200～300 ℃, adjusting is added in direct voltage between fog-spray nozzle and substrate to obtaining stabilized uniform spraying, according to the time of the THICKNESS CONTROL spraying of required film.
General control spraying 30-180 minute, thickness of deposited film is the 1-200 micron.
Described substrate material comprises porous foam nickel, Copper Foil or gold-plated monocrystalline silicon piece.
Compared with prior art,, need not special atmosphere protection, in normal temperature air, can operate, simplified operating procedure because the inventive method utilizes the electrostatic spray precipitation equipment to prepare film; The present invention is earlier with lithium acetate: cobalt acetate is by 0.25-4: 1 mixed in molar ratio, be dissolved in that to obtain metal cation concentration in the carbitol solvent be 0.001-0.02 mol precursor solution, with this precursor solution with 2-4 milliliter/when hour at the uniform velocity flowing to fog-spray nozzle, can in bigger voltage range, obtain stable spraying, not only can make the film of distributed components, and good reproducibility; If the nickel foam of selecting porous for use helps the infiltration of electrolyte more as substrate; Substrate constant temperature is at 200～300 ℃, can make and be deposited on the three dimensional network pore structure that on-chip spraying forms uniqueness, this structure has strengthened the power that is connected of film and substrate, makes electrode film can not come off from substrate in charge and discharge process, has improved the cycle performance of electrode; The thickness of deposited film is determined by spray time, thereby film thickness can be controlled arbitrarily; Pulsed laser deposition (PLD) that the prior art for preparing lithium-ion film cell negative pole adopts or sputtering method need just can use behind the film double sintering with preparation, can directly be used as lithium-ion film cell negative pole and the film for preparing among the present invention need not reprocessing, reduce production cost.
The XLi that the inventive method is prepared
2(X: Y=0.125-2: 1) composite oxide film can be used as lithium-ion film cell negative pole to OYCoO.Li
2The existence of O is not only for the embedding of lithium ion with take off embedding more interface is provided, and it can become the cobalt oxidation of divalence the cobalt of trivalent gradually in charge and discharge process, and the raising of the valence state of cobalt makes that the gain and loss electron number increases in the redox reaction process.Because the discharge capacity of battery is directly proportional with gain and loss electron number in the redox reaction process, so along with the increasing of the period of battery, the discharge capacity of battery increases gradually; The cobaltic-cobaltous oxide negative pole film trivalent cobalt after discharge first that has overcome prior art use pulsed laser deposition (PLD) preparation is reduced and becomes the capacitance loss that the divalence cobalt causes, has prolonged the cycle life of battery.
Description of drawings:
The XLi that Fig. 1 makes for embodiment 1
2The X-ray diffractogram of the copper target incident of OYCoO composite oxides;
The XLi that Fig. 2 makes for embodiment 2
2The X-ray diffractogram of the copper target incident of OYCoO composite oxides.
The XLi that Fig. 3 makes for embodiment 1
2The OYCoO stereoscan photograph;
The XLi that Fig. 4 makes for embodiment 2
2The OYCoO stereoscan photograph.
Fig. 5 for each embodiment make membrane electrode and lithium metal form half-cell under the condition of 1C discharge cycle-index to specific discharge capacity figure.
Fig. 6 forms the specific volume spirogram of half-cell under different discharge rates for each embodiment makes membrane electrode with lithium metal.
The graph of a relation of lithium and cobalt ratio in the specific discharge capacity of membrane electrode that Fig. 7 makes for embodiment 3 and lithium metal composition half-cell and the precursor liquid.
Embodiment:
Embodiment 1:
The electrostatic spray precipitation equipment that uses among assembling the present invention earlier: 0.8 millimeter silicone tube one end of internal diameter is put into 250 milliliters conical flask containing precursor liquid, the other end connects 0.4 millimeter syringe needle of a pin hole internal diameter, then silicone tube is fixed in the flowtube groove of peristaltic pump, control flows weight range 0-50 milliliter/hour, voltage range is that the positive wire folder of the high voltage direct current generator of 0-40000V is connected in syringe needle and keeps needle point straight up, thermocouple of 1-4 centimeters horizontal positioned directly over the needle point, 0-800 ℃ of temperature control scope, the high voltage direct current generator negative pole is connected in thermocouple.
Prepare precursor solution then: prepare precursor solution then: get 0.0255 gram LiOAC2H respectively
2O and 0.6227 gram Co (OAC)
2.4H
2O (be Li: the Co mol ratio is 1: 1) places 250 milliliters of conical flasks, measures the 50mL carbitol with graduated cylinder and pours fully dissolving of stirring in the conical flask into.With a diameter that has been weighed as 69.8 milligrams is that 14 millimeters round nickel foam substrate is fixed in thermocouple, and needle point and substrate are treated to keep constant temperature after the thermocouple heating makes substrate temperature rise to 235 ℃ apart from keeping 2.5 centimetres; Control peristaltic pump flow valve, make silicone tube with 3 milliliters/time speed from conical flask, extract precursor solution.When treating flow of liquid to needle point, regulate and be added in dc high-voltage source between needle point and substrate, when voltage was 8.3kV, needle point place liquid was stable mist and is deposited on the round nickel foam substrate.After the successive sedimentation 2 hours, obtain the XLi of black
2(weighing heavily is 71.2 milligrams to OYCoO for X=0.5, Y=1) composite oxide film electrode.
Determine XLi by X-ray diffractometer
2OYCoO crystalline composite oxide structure: curve is the X-ray diffraction light spectrogram of embodiment 1 resultant compound among Fig. 1, at 45 °, 65 ° and 77 ° three sharp-pointed diffraction maximums are arranged among the figure, diffraction maximum for substrate, near the diffraction maximum that four broads are arranged 36 °, 42.5 °, 61.5 ° and 74 °, be respectively (111), (200), (220) and (311) face of the CoO of crystallite attitude, wherein 2 θ are that the peak relative intensity ratio of 42.5 ° and 36 ° is 1: 1.45.When keeping 235 ℃ because of substrate again, LiOAC2H
2It is Li that O decomposes the product that obtains
2O, visible Li
2O is unformed form; Because of Li in the precursor liquid: the Co mol ratio is 1: 1, according to conservation of matter principle, so the composite oxides composition that obtains is XLi
2OYCoO (X=0.5, Y=1).
Measured the microstructure of membrane electrode by ESEM: Fig. 3 is the stereoscan photograph of this electrode film, has adhered to the poroid electrode film of one deck three dimensional network as seen from the figure on the nickel foam substrate, and the mesh size is the 5-30 micron, and film thickness is 30 microns.
The lithium battery system that adopts bipolar electrode to form, measure the charge and discharge cycles of electrode: with the high purity lithium sheet as negative pole, XLi
2(X=0.5, Y=1) the composite oxide film electrode is as positive pole, 1 mol LiPF for OYCoO
6+ EC+DEC (EC and DEC volume ratio are 1: 1) is as electrolyte, and battery is assemblied in the glove box of applying argon gas and carries out, and the battery charging and discharging test is being carried out on new prestige (Neware) battery test system.
Curve a above among Fig. 5 is that the electrode film of present embodiment 1 lies prostrate at voltage range 3.00-0.01, when discharge rate is 1C, and period and specific discharge capacity graph of a relation.Peak is first discharge specific capacity 780mAh/g on the curve, the discharge capacity loss late is 13% first, increase gradually along with period, capacity is also risen progressively gradually, capacity surpasses discharge capacity first after 100 circulations, reaches 788mAh/g, and the valence state of visible cobalt raises in the process of circulation to some extent, the specific discharge capacity of the battery that makes raises, and this shows and consists of XLi
2(X=0.5, Y=1) electrode film has excellent cycle performance to OYCoO.
Curve c above among Fig. 6 is that the electrode film of present embodiment 1 lies prostrate at voltage range 3.00-0.01, discharge capacity under the different discharge rates changes, when discharge rate was respectively 0.1C, 0.2C, 1C, 2C and 5C, discharge capacity was respectively 856mAh/g, 842mAh/g, 745mAh/g, 710mAh/g and 650mAh/g.As seen electrode film still has higher discharge capacity when high current charge-discharge.
Embodiment 2:
Get 0.0255 gram LiOAC2H respectively
2O and 0.6227 gram Co (OAC)
24H
2O (be Li: the Co mol ratio is 1: 1), in the 50mL carbitol, stir fully dissolving, adopt and embodiment 1 identical operations step, with Copper Foil as substrate, heated substrate to temperature is 245 ℃ and obtains electrode film in the insulation of this temperature, deposition after 2 hours, is assembled into its performance of test behind the battery.
Fig. 2 is the X-ray diffraction light spectrogram of the copper target incident of the resultant compound of present embodiment, at 44 °, 52 ° and 75 ° three sharp-pointed diffraction maximums are arranged among the figure, diffraction maximum for substrate, near the diffraction maximum that four broads are arranged 36 °, 42.5 °, 61.5 ° and 74 °, be respectively (111), (200), (220) and (311) face of CoO, wherein 2 θ are that the peak relative intensity ratio of 42.5 ° and 36 ° is 1: 1.53; Know LiOAC2H by embodiment 1
2O is decomposed into the Li of unformed shape
2O, because of Li in the precursor liquid: the Co mol ratio is 1: 1, according to conservation of matter principle, so the composite oxides composition that obtains is XLi
2OYCoO (X=0.5, Y=1).
As seen Fig. 4 is the stereoscan photograph of electrode film, and the film that obtains during as substrate at the Copper Foil of densification is mesh-structured, and the mesh size is the 2-20 micron, and film thickness is 10 microns.
The curve b of below is that the electrode film that present embodiment prepares lies prostrate at voltage range 3.00-0.01 among Fig. 5, and cycle-index is to the relation curve of discharge capacity under the condition of 1C discharge.Peak is first discharge specific capacity 640mAh/g on the curve, and the discharge capacity loss late is 15% first, and along with the increase gradually of period, capacity is also risen progressively gradually, and discharge capacity is 660mAh/g after 100 circulations.
The curve d of below is that the electrode film that present embodiment prepares lies prostrate at voltage range 3.00-0.01 among Fig. 6, discharge capacity under the different discharge rates changes, when discharge rate was respectively 0.1C, 0.2C, 1C, 2C and 5C, discharge capacity was respectively 780mAh/g, 685mAh/g, 645mAh/g, 603mAh/g and 400mAh/g.
Embodiment 3:
Get LiOAC2H respectively
2O and Co (OAC)
24H
2O is 0.25: 1,0.5: 1,1: 1,2: 1 and five parts of solution of preparation in 4: 1 with Li: Co, and Co concentration is 0.005 mol in every part of solution, and solvent is 50 milliliters of carbitols.Adopt the step identical, still select nickel foam, make substrate maintenance constant temperature at 225 ℃ as substrate with embodiment 1, deposit 2 hours respectively after, obtain five kinds of chemical compositions and be respectively XLi
2OYCoO (X=0.125, Y=1), XLi
2OYCoO (X=0.25, Y=1), XLi
2OYCoO (X=0.5, Y=1), XLi
2OYCoO (X=1, Y=1) and XLi
2(X=2, electrode film Y=1) are assembled into its performance of test behind the battery with the gained electrode film to OYCoO.
Fig. 7 lies prostrate the capacity during the 1C discharge rate for the electrode film of present embodiment preparation at voltage range 3.00-0.01.When Li: Co was 0.25: 1,0.5: 1,1: 1,2: 1 and 4: 1, the discharge capacity of electrode film was respectively 480mAh/g, 550mAh/g, 760mAh/g, 470mAh/g and 280mAh/g.
As seen from the above embodiment: the present invention adopts the XLi of electrostatic spray sedimentation preparation
2(X: Y=0.125-2: 1) the composite oxide film electrode has higher specific capacity, low irreversible capacity loss first and excellent cycle performance as lithium-ion film cell negative pole to OYCoO.
Claims (3)
1. a lithium-ion film cell negative pole is characterised in that it is the XLi of thickness 1-200 micron
2OYCoO composite oxide film, wherein X: Y=0.125-2: 1; Film is a tridimensional network, and the size of mesh is the 2-30 micron; Li wherein
2The structure of O and CoO is respectively amorphous state and crystallite attitude; 2 θ of the X ray characteristic peak that the incident of copper target produces are 36 °, 42.5 °, 61.5 ° and 74 °, and its 2 θ is that the peak relative intensity ratio of 42.5 ° and 36 ° is 1: 1-1.7.
2. the preparation method of a lithium-ion film cell negative pole, it is characterized in that lithium acetate: cobalt acetate is by 0.25-4: 1 mixed in molar ratio, be dissolved in the carbitol solvent, forming metal cation concentration is the precursor solution of 0.001-0.02 mol, with this solution with 2-4 milliliter/hour at the uniform velocity flow to fog-spray nozzle, the adjusting fog-spray nozzle is 1-4 centimetre to the distance of substrate, control heated substrate constant temperature is at 200～300 ℃, adjusting is added in direct voltage between fog-spray nozzle and substrate to obtaining stabilized uniform spraying, according to the time of the THICKNESS CONTROL spraying of required film.
3. as the preparation method of lithium-ion film cell negative pole as described in the claim 2, be characterised in that described substrate material comprises porous foam nickel, Copper Foil or gold-plated monocrystalline silicon piece.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100544083C (en) * | 2007-02-26 | 2009-09-23 | 中国科学技术大学 | A kind of lithium-ion film cell negative pole and preparation method thereof |
| CN101222047B (en) * | 2008-01-14 | 2010-12-29 | 浙江大学 | Cathode material of thin film lithium ion battery and method for producing the same |
| CN102456928B (en) * | 2011-07-20 | 2014-10-08 | 宁波大学 | Spray pyrolysis battery manufacturing method of double-layer film all-solid-state film lithium battery |
| CN102299383B (en) * | 2011-07-20 | 2012-12-19 | 宁波大学 | Mist pyrolysis preparation method of all-solid-state film lithium battery |
| CN103996821A (en) * | 2014-06-14 | 2014-08-20 | 哈尔滨工业大学 | Negative film for lithium ion secondary battery as well as preparation method and application of negative film |
| CN109599558B (en) * | 2018-10-09 | 2022-06-07 | 全球能源互联网研究院有限公司 | Method for preparing Prussian blue positive electrode material and sodium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188564A (en) * | 1996-04-16 | 1998-07-22 | 松下电器产业株式会社 | Cathodic active material and seconday battery using the same |
| CN1225518A (en) * | 1998-01-30 | 1999-08-11 | 佳能株式会社 | Lithium secondary battery and method of mfg. lithium secondary battery |
| EP1275442A1 (en) * | 2001-07-13 | 2003-01-15 | Stichting voor de Technische Wetenschappen | Electrostatic spray deposition (ESD) of biocompatible coatings on metallic substrates |
| CN1567620A (en) * | 2003-06-25 | 2005-01-19 | 南都瑞宝能源科技（上海）有限公司 | Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188564A (en) * | 1996-04-16 | 1998-07-22 | 松下电器产业株式会社 | Cathodic active material and seconday battery using the same |
| CN1225518A (en) * | 1998-01-30 | 1999-08-11 | 佳能株式会社 | Lithium secondary battery and method of mfg. lithium secondary battery |
| EP1275442A1 (en) * | 2001-07-13 | 2003-01-15 | Stichting voor de Technische Wetenschappen | Electrostatic spray deposition (ESD) of biocompatible coatings on metallic substrates |
| CN1567620A (en) * | 2003-06-25 | 2005-01-19 | 南都瑞宝能源科技（上海）有限公司 | Anode material--lithium nickelate cobalt for lithium ion battery and preparation method thereof |
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