CN100570015C - A kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material - Google Patents
A kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material Download PDFInfo
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- CN100570015C CN100570015C CNB2007100089994A CN200710008999A CN100570015C CN 100570015 C CN100570015 C CN 100570015C CN B2007100089994 A CNB2007100089994 A CN B2007100089994A CN 200710008999 A CN200710008999 A CN 200710008999A CN 100570015 C CN100570015 C CN 100570015C
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Abstract
The present invention relates to a kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material.This method is electroplated by modified layer and the galvanized two step electroplating processs of active layer are formed.Wherein: the modified layer electroplate liquid is by nickelous chloride 50-280g, cobalt chloride 10-180g, and boric acid 1-50g and distilled water 800-900mL form, and temperature 20-75 ℃, electroplating time 0.2-30 minute; The active layer electroplate liquid is by sodium stannate 5-60g, sodium hydroxide 5-60g, and sodium-acetate 5-50g and distilled water 800-900mL form, and temperature 40-80 ℃, electroplating time is 0.2-50 minute.Two steps electroplated all at 0.1-1.5A/dm
2Carry out under interval arbitrary current density.Raw materials cost of the present invention is lower, and raw material sources are extensive, and preparation process is simple, and is consuming time few.This electrode materials has outstanding discharge performance and charge and discharge cycles stability, loading capacity is up to more than the active goods and materials of 400mAh/g first, cycle performance is good, is expected to be applied to lithium ion battery, lithium cell, polymer Li-ion battery, particularly the film-type battery.
Description
Technical field
The present invention relates to a kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material, the alloy that utilizes this method preparation particularly has important use in film-type lithium ion battery field in field of batteries.
Technical background
Along with the continuous release of removable electronic product, more and more higher to the performance requriements of lithium ion battery, quantitative requirement is more and more.The commodity lithium ion battery negative material is based on graphitized carbon material at present.The shortcoming of this material is that the SEI film that generates that discharges first can cause higher irreversible capacity loss.At high temperature graphitized carbon material may decompose because of protective layer, causes battery failure or causes safety issue.The theoretical specific capacity of the potential substitute as the graphitized carbon negative material---metallic tin negative material can reach 990mAh/g (Li
4.4Sn).This theoretical specific capacity is more than the twice of theoretical specific capacity of graphitized carbon material.These advantages make metallic tin and tin base cathode material become the negative material of future generation of people's expectation.Yet in actual use, the metallic tin negative material reaches more than 358% at the cubical expansivity that discharges and recharges embedding, deviate from lithium ion, first round-robin irreversible capacity height.After circulation several times, powder phenomenon-tion takes place in metallic tin negative pole easily.Realize the practical application and the commercialization of tin negative pole material, must bring into play the high theoretical specific capacity advantage of tin negative pole, improve its cycle performance.
In order to improve the performance of tin negative pole material, according to the viewpoint of " Buffer Matrix ", can in Sn, add inactive soft metal M, make soft metal M and Sn form the SnM alloy.When in this alloy, embedding lithium, when forming the LiSnM alloy, because the ductility of M can make the volume change of Sn reduce greatly.For this reason after deliberation SnSb[Yang J., Takeda Y., Imanishia N., et al.Solid State Ionics, 2000,133 (3-4): 189-194], Mg
2Sn[Kim H., Kim Y.-J., Kim D.G., et al.Solid StateIonics, 2001,144 (1-2): 41-49], SnCo[Guo H., Zhao H.L., Jia X., et al., Electrochim.Acta, 2007,52 (14): 4853-4857], SnMnC[Beaulieu L., D., Larcher R., Dunlap A., et al.J.Alloys ﹠amp; Compounds, 2000,297 (1-2): 122-128], SnFe[Mao O., Dunlap R.A., Dahn J.R., Solid State Ionics, 1999,118 (1-2): 99-109], SnZrAg[Kim Y.-L., Lee S.-J., Baik H.-K.et al., J Power Sources, 2003,119-121:106-109], SnZnCu[Wang L., Kitamura S., Obata K., et al., J.Power Sources, 2005,141 (2): 286-292], SnNi (KeF., Huang L., Jiang H., et al.Electrochem.Commun, 2007,9 (2): 228-232) wait tin base alloy anode material.Ahn etc. [Ahn J H, Kim Y J, Wang G, et al.MaterialsTransactions, 2002,43 (1): 63-6670] find the nanometer Ni of high-energy ball milling method preparation
3Sn
2The loading capacity first of alloy is up to 1520mAh/g.But the cycle performance of this material is very poor.40 times circulation back loading capacity is only surplus less than 35mAh/g.Have preparation condition and control easily because electrochemical plating prepare tin-based alloy, cheap, raw materials used have advantages such as multiple scheme is available, carried out some research work.As, Mukaibo etc. [Mukaibo H., Momma T., Osaka T., J.Power Sources, 2005,146 (1-2): 457-463] have prepared the SnNi alloy material of cathode with electro-plating method.[Yang J., Winter M., Besenhard J.O., Solid State Ionics, 1996,90:281-287 such as Yang; Besenhard J.O., Yang J., Winter M., J.Power Sources, 1997,68:87-90; Yang J., Wachtler M., Winter M., et al.Electrochem.﹠amp; Solid State Lett., 1999,2 (4): 161-163; Yang J., Takeda Y., Imanishi N., et al.J.Electrochem.Soc., 1999,146:4009-4013] prepared the SnSb alloy material of different-grain diameter respectively with electrochemical deposition and chemical reduction method.When they find that SnSb alloying pellet when preparation is less than 300nm, 200 circulations afterwards the loading capacity of samples can also reach 360mAh/g.Studies show that although through above improvement effort, these tin base cathode materials still manifest bigger cubical expansivity in the charge and discharge cycles process, capacity attenuation is bigger, and particularly the round-robin irreversible capacity is big first.In order to improve the cycle performance of tin-based alloy, the present invention adopted for two steps electroplated and is prepared.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material.For achieving the above object, the technical solution adopted in the present invention is: be made up of modified layer plating and the galvanized two step electroplating processs of active layer.In the preparation, adopt and earlier copper sheet to be put into the modified layer plating bath for preparing in advance and electroplate, the copper sheet that will coat nickel cobalt (alloy) is again put into the active layer plating bath for preparing in advance and is electroplated; Perhaps earlier copper sheet is put into the active layer plating bath for preparing in advance and electroplated, the copper sheet that will coat the tin film is again put into the modified layer plating bath for preparing in advance and is electroplated.
(1) preparation (weightmeasurement ratio) of modified layer plating and electroplate liquid
Nickelous chloride 50-280g
Cobalt chloride 10-180g
Boric acid 1-50g
Distilled water 800-900mL
With not galvanized copper sheet or earlier to place temperature through the galvanized copper sheet of active layer be 20-75 ℃ electroplate liquid, at 0.1-1.5A/dm
2Under interval arbitrary current density, electroplated 0.2-30 minute in negative electrode with direct current.
(2) preparation (weightmeasurement ratio) of active layer plating and electroplate liquid
Sodium stannate 5-60g
Sodium hydroxide 5-60g
Sodium-acetate 5-50g
Distilled water 800-900mL
With not galvanized copper sheet or earlier to place temperature through the galvanized copper sheet of modified layer be 40-80 ℃ of electroplate liquid, at 0.1-1.5A/dm
2Under interval arbitrary current density, electroplated 0.2-50 minute with direct current in negative electrode.
Compare with other inventive method, raw materials cost of the present invention is lower, and raw material sources are extensive, and preparation process is simple, and is consuming time few.This electrode materials has outstanding discharge performance and charge and discharge cycles stability, loading capacity is up to more than the active goods and materials of 400mAh/g first, cycle performance is good, be expected to be applied to lithium ion battery, lithium cell, polymer Li-ion battery, particularly film-type (as thickness at 0.1-1000 μ m) battery.
Embodiment
Below in conjunction with embodiment the present invention is further detailed.Embodiment further replenishes and explanation of the present invention, rather than the restriction to inventing.
Embodiment 1
(1) preparation of modified layer plating and electroplate liquid
With nickelous chloride 50g, cobalt chloride 180g and boric acid 1g by weight volume ratio be dissolved in the distilled water of 900mL, the control temperature of electroplating solution is 20 ℃.
Copper sheet is placed electroplate liquid, at 0.1A/dm
2Direct current under, electroplated 30 minutes in negative electrode, obtain coating the copper sheet of nickel cobalt (alloy) rete.
(2) preparation of active layer plating and electroplate liquid
With sodium stannate 5g, sodium hydroxide 5g and sodium-acetate 5g by weight volume ratio be dissolved in the 800mL distilled water, the control temperature of electroplating solution is 40 ℃.
Clean being placed on of the copper sheet that coats the nickel cobalt (alloy) rete activated in the plating bath, at 0.1A/dm
2Direct current under, electroplated 50 minutes in negative electrode, obtain tin-copper-nickel-cobalt alloy cathode material.
Embodiment 2
(1) preparation of modified layer plating and electroplate liquid
With nickelous chloride 280g, cobalt chloride 10g and boric acid 10g by weight volume ratio be dissolved in the 900mL distilled water, the control temperature of electroplating solution is 40 ℃.
Copper sheet is placed plating bath, at 0.5A/dm
2Direct current under, electroplated 5 minutes in negative electrode, make the copper sheet that coats the nickel cobalt (alloy) rete.
(2) preparation of active layer plating and electroplate liquid
With sodium stannate 30g, sodium hydroxide 30g and sodium-acetate 20g volume ratio by weight are dissolved in the 900mL distilled water, and the control temperature of electroplating solution is 60 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete cleaned being placed in the active layer plating bath, is 0.5A/dm in current density
2Direct current under, electroplated 30 minutes in negative electrode, make tin-copper-nickel-cobalt alloy cathode material.
Embodiment 3
(1) preparation (weightmeasurement ratio) of modified layer plating and electroplate liquid
With nickelous chloride 140g, cobalt chloride 90g and boric acid 30g by weight volume ratio be dissolved in the 900mL distilled water, the control temperature of electroplating solution is 75 ℃
Copper sheet is placed plating bath, at 1.5A/dm
2Direct current under, electroplated 0.2 minute in negative electrode, make the copper sheet that coats the nickel cobalt (alloy) rete.
(2) preparation of active layer plating and electroplate liquid
With sodium stannate 60g, sodium hydroxide 50g and sodium-acetate 30g by weight volume ratio be dissolved in the 800mL distilled water, the control bath temperature is 60 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete cleaned being placed in the electroplate liquid, is 0.1A/dm in current density
2Direct current under, electroplated 30 minutes in negative electrode, make tin nickel cobalt-copper alloy negative material.
Embodiment 4
(1) preparation of modified layer plating and electroplate liquid
With nickelous chloride 280g, cobalt chloride 180g and boric acid 50g by weight volume ratio be dissolved in the 800mL distilled water, the control bath temperature is 75 ℃
Copper sheet is placed electroplate liquid, is 0.6A/dm in current density
2The negative electrode direct current under, electroplated 3 minutes in negative electrode, make the copper sheet that coats the nickel cobalt (alloy) rete.
(2) preparation of active layer plating and electroplate liquid
With sodium stannate 60g, sodium hydroxide 60g and sodium-acetate 50g by weight volume ratio be dissolved in the 900mL distilled water, the control bath temperature is 80 ℃.
The copper sheet that coats the nickel cobalt (alloy) rete cleaned be placed in the active layer electroplate liquid, at 1.5A/dm
2Direct current under, electroplated 3 minutes in negative electrode, make tin-copper-nickel-cobalt alloy cathode material.
Embodiment 5
(1) preparation of active layer plating and electroplate liquid
With sodium stannate 50g, sodium hydroxide 30g and sodium-acetate 30g by weight volume ratio be dissolved in the 900mL distilled water, the control bath temperature is 75 ℃.
Copper sheet is placed electroplate liquid, at 0.6A/dm
2Direct current under, electroplated 15 minutes in negative electrode, obtain coating the copper sheet of tin layer.
(2) preparation of the plating of modified layer and electroplate liquid
With nickelous chloride 50g, cobalt chloride 50g and boric acid 20g by weight volume ratio be dissolved in the 800mL distilled water, the control bath temperature is 75 ℃.
The copper sheet that has coated the tin film cleaned be placed in the modified layer electroplate liquid, at 1.5A/dm
2Direct current under, electroplated 1 minute in negative electrode, make tin-copper-nickel-cobalt alloy cathode material.
Claims (1)
1, a kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material is characterized in that the preparation method who is taked carries out direct current electrode position for earlier copper sheet being put into the modified layer plating bath, and putting into the active layer plating bath again carries out direct current electrode position; Perhaps earlier copper sheet is put into the active layer plating bath and carry out direct current electrode position, put into the modified layer plating bath again and carry out direct current electrode position;
Wherein:
(1) the modified layer temperature of electroplating solution is 20-75 ℃, and electroplating time is 0.2-30min, and the galvanic current density of negative electrode is 0.1-1.5A/dm
2
(2) the active layer temperature of electroplating solution is 40-80 ℃, and electroplating time is 0.2-50min, and the galvanic current density of negative electrode is 0.1-1.5A/dm
2
(3) proportioning of modified layer electroplate liquid is
Nickelous chloride 50-280g, cobalt chloride 10-180g, boric acid 1-50g, distilled water 800-900mL;
(4) proportioning of active layer electroplate liquid is
Sodium stannate 5-60g, sodium hydroxide 5-60g, sodium-acetate 5-50g, distilled water 800-900mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100089994A CN100570015C (en) | 2007-05-23 | 2007-05-23 | A kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material |
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| CNB2007100089994A CN100570015C (en) | 2007-05-23 | 2007-05-23 | A kind of method of utilizing the plating of two steps to prepare tin-copper-nickel-cobalt alloy cathode material |
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| CN100570015C true CN100570015C (en) | 2009-12-16 |
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| WO2013005774A1 (en) * | 2011-07-07 | 2013-01-10 | 東洋鋼鈑株式会社 | Surface-treated steel sheet for battery case, process for producing same, battery case, and battery |
| CN112176372B (en) * | 2020-09-27 | 2021-10-15 | 东北大学 | Method for preparing cobalt-tantalum alloy coating at low temperature by taking cobalt dichloride and tantalum pentachloride as raw materials |
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Non-Patent Citations (2)
| Title |
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| 电镀手册 上册. 张允诚，胡如南，向荣，411-413，578-579，国防工业出版社. 1997 |
| 电镀手册 上册. 张允诚，胡如南，向荣，411-413，578-579，国防工业出版社. 1997 * |
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