CN100526516C - preparation process of Sn-Cu alloy material for negative pole of lithium ion cell - Google Patents

preparation process of Sn-Cu alloy material for negative pole of lithium ion cell Download PDF

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CN100526516C
CN100526516C CNB2006101113159A CN200610111315A CN100526516C CN 100526516 C CN100526516 C CN 100526516C CN B2006101113159 A CNB2006101113159 A CN B2006101113159A CN 200610111315 A CN200610111315 A CN 200610111315A CN 100526516 C CN100526516 C CN 100526516C
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lithium ion
negative pole
ion cell
mixing solutions
alloy
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CN1974869A (en
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孙世刚
樊小勇
黄令
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Xiamen University
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Abstract

The present invention relates to negative pole material for lithium ion cell, and is especially one no-cyanide electroplating process for preparing Sn-Cu alloy as negative pole material for lithium ion cell. The no-cyanide electroplating process includes the following steps: dissolving potassium pyrophosphate in water, adding stannous chloride and copper sulfate to obtain mixed solution, adding epoxy chloroalkane, triethanolamine, formaldehyde and gelatin to form electroplating solution; and electroplating on copper substrate to form silvery white bright Sn-Cu alloy. The process has low cost, no environmental pollution, and the lithium ion cell with negative pole of the Sn-Cu alloy has high initial capacity, high initial charging and discharging efficiency and good charging and discharging circulating performance.

Description

The preparation method of Sn-Cu alloy material for negative pole of lithium ion cell
Technical field
The present invention relates to a kind of lithium ion battery negative material, particularly relate to and a kind ofly adopt non-prussiate to electroplate the method for preparing Sn-Cu alloy material for negative pole of lithium ion cell.
Technical background
Tin has high Theoretical Mass specific storage (990mAh/g) and volume and capacity ratio (7200Ah/L) as lithium ion battery negative material, and safety performance is good simultaneously, receives increasing research and concern.Tin as the subject matter of lithium ion battery negative material is, embeds and to deviate from the process volume change very big at lithium ion, causes charge-discharge performance bad.The alloy of tin can be alleviated volumetric expansion in tin and the lithium alloyage process to a certain extent as lithium ion battery negative material, reaches the purpose that improves the material cycle performance.
The alloy that extensively is studied at present mainly contains Sn-Cu, Sn-Zn, Sn-Sb and Sn-Co etc., and wherein the Sn-Cu alloy is considered to the most rising alloy material, referring to document: (1) Electrochimica Acta 45 (1999): 31-50; (2) J.Mater.Chem., 2001,11:1502-1505; (3) J.Electrochem.Soc., 2005,152 (3): A560-A565; (4) J.Power Sources, 1999,81-82:383-387.1999, and Kepler etc. (J.powerSources, 1999,81-82:383-387) at first reported Cu 6Sn 5The application of alloy in lithium ion battery negative material.Discover Cu 6Sn 5Has the initial capacity of 350mAh/g with the lithium reversible reaction.Kim etc. (J.Power Sources, 2002,104:221-225) method by chemical reduction makes Cu 6Sn 5Alloy, its cycle performance is with respect to adopting high temperature sintering and mechanical ball milling method gained alloy to improve a lot.
Electro-plating method has the characteristics of the simple and easy large-scale production of technology, is widely used in the alloy preparation.(J.Electrochem.Soc., 2003,150 (7): A894-A898) at first use the method for pulse electrodeposition to obtain Cu such as Dahn 6Sn 5Alloy, and studied its performance as lithium ion battery negative material.Though this method can obtain Cu 6Sn 5Alloy, but the method for pulse electrodeposition is difficult for accurately control alloy composition, difficult scale preparation.Tamura etc. (J.Power sources, 2002,107:48-55) adopt the method for galvanic deposit in the copper substrate, to deposit thin film tin, obtain Sn, Cu through Overheating Treatment then 3Sn and Cu 6Sn 5Combined electrode, the charge-discharge performance of this combined electrode has obtained raising to a certain degree before with respect to thermal treatment.Pu etc. (Electrochimica Acta, 2005,50:4140-4145) galvanic deposit one deck Sn on substrate copper coats layer of copper then, obtains Sn, Cu through Overheating Treatment 3Sn and Cu 6Sn 5Combined electrode.Result of study shows that coating copper improves before coating with the charge-discharge performance of rear electrode.
Summary of the invention
The objective of the invention is at its step of method of existing preparation Sn-Cu alloy material for negative pole comparatively complicated; be difficult for problems such as large-scale production; provide a kind of pollution-free; cost is low; initial capacity is big, and first charge-discharge efficiency non-prussiate high and good cycle is electroplated the method that preparation is mainly used in the Sn-Cu alloy material for negative pole of lithium ion battery.
Step of the present invention is as follows:
1) potassium pyrophosphate is dissolved in the water, under condition of stirring, adds tin protochloride (SnCl respectively 22H 2O) and copper sulfate (CuSO 45H 2O), get mixing solutions, the concentration of potassium pyrophosphate is 100～400g/L, and the concentration of tin protochloride is 5～25g/L, and the concentration of copper sulfate is 3～8g/L;
2) in mixing solutions, add additive, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 0.5～1g/L, trolamine 0.5～1g/L, formaldehyde 0.50～1g/L, gelatin 0.02～0.10g/L gets electroplate liquid;
3) at 0.5～1A/dm 2Under current density and the stirring condition, be that 1～10min is electroplated in substrate in electroplate liquid, form silvery white bright coating, promptly obtain gun-metal with the copper sheet.
The gun-metal of above-mentioned gained can be used as the negative material of lithium ion battery.
Compare with existing method, outstanding advantage of the present invention is:
1. the utilization electric plating method prepares lithium ion battery negative material, can accomplish scale production;
2. use non-cyanide solution to be electroplate liquid, environmentally safe;
3. in the gun-metal with method preparation of the present invention, tin is that activeconstituents, copper are frame material, as frame material, can partly alleviate the volume change of tin in charge and discharge process with copper, thereby reaches the purpose that improves the electrode materials charge-discharge performance.
4. prepare Sn-Cu alloy material for negative pole of lithium ion cell with method of the present invention, not only the electroplate liquid cost is low, and the cost of relative other tin-based alloys of tin copper alloy material is also lower.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure that the embodiment of the invention 3 is electroplated the gained gun-metal, and in Fig. 1, X-coordinate is sweep limit (2-Theta), and ordinate zou is diffracted intensity (Intensity a.u.), and mark is followed successively by Cu from top to bottom 6Sn 5, Sn.
Fig. 2 is scanning electron microscope (SEM) figure that the embodiment of the invention 3 is electroplated the gained gun-metal.In Fig. 2, scale is 2 μ m.
Fig. 3 is the charging and discharging curves of the embodiment of the invention 3 gained gun-metal electrodes under the 100mA/g electric current.In Fig. 3, X-coordinate is charging capacity (capacity)/(mAh/g), and ordinate zou is current potential (Potential)/(E, vs.Li +/ Li), each curve is respectively 50th from left to right, 20th, 1th, 5th.
Fig. 4 is the comparison of the charge-discharge performance of the embodiment of the invention 3 gained gun-metals and pure tin electrode.In Fig. 4, X-coordinate is cycle number (Cycle number), and ordinate zou is charging capacity (capacity)/(mAh/g), and mark is followed successively by Sn-Cu, Sn from top to bottom.
Fig. 5 is the efficiency for charge-discharge (Coulomb effeciency) of the embodiment of the invention 3 gained gun-metals.In Fig. 5, X-coordinate is cycle number (Cycle number), and ordinate zou is coulombic efficiency (Coulomb Efficiency)/(%).
Embodiment
Embodiment 1
Potassium pyrophosphate is dissolved in the deionized water, adds tin protochloride and copper sulfate respectively under condition of stirring, get mixing solutions, the concentration of potassium pyrophosphate is 100g/L, and the concentration of tin protochloride is 10g/L, and the concentration of copper sulfate is 5g/L.Add additive in mixing solutions, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, and the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 0.7g/L, trolamine 0.8g/L, formaldehyde 0.5g/L, gelatin 0.03g/L gets electroplate liquid.At 0.7A/dm 2Under current density and the stirring condition, be that 5min is electroplated in substrate in electroplate liquid, form silvery white bright coating, promptly obtain gun-metal with the copper sheet.
Embodiment 2
Potassium pyrophosphate is dissolved in the deionized water, adds tin protochloride and copper sulfate respectively under condition of stirring, get mixing solutions, the concentration of potassium pyrophosphate is 200g/L, and the concentration of tin protochloride is 15g/L, and the concentration of copper sulfate is 6g/L.Add additive in mixing solutions, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, and the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 1g/L, trolamine 0.7g/L, formaldehyde 0.7g/L, gelatin 0.05g/L gets electroplate liquid.At 0.8A/dm 2Under current density and the stirring condition, be that 7min is electroplated in substrate in electroplate liquid, form silvery white bright coating, promptly obtain gun-metal with the copper sheet.
Embodiment 3
Potassium pyrophosphate is dissolved in the distilled water, adds tin protochloride and copper sulfate respectively under condition of stirring, get mixing solutions, the concentration of potassium pyrophosphate is 300g/L, and the concentration of tin protochloride is 25g/L, and the concentration of copper sulfate is 3g/L.Add additive in mixing solutions, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, and the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 0.8g/L, trolamine 0.5g/L, formaldehyde 1g/L, gelatin 0.1g/L gets electroplate liquid.At 0.5A/dm 2Under current density and the stirring condition, be that 1min is electroplated in substrate in electroplate liquid, form silvery white bright coating, promptly obtain gun-metal with the copper sheet.
Embodiment 4
Potassium pyrophosphate is dissolved in the distilled water, adds tin protochloride and copper sulfate respectively under condition of stirring, get mixing solutions, the concentration of potassium pyrophosphate is 400g/L, and the concentration of tin protochloride is 5g/L, and the concentration of copper sulfate is 8g/L.Add additive in mixing solutions, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, and the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 0.5g/L, trolamine 1g/L, formaldehyde 0.8g/L, gelatin 0.02g/L gets electroplate liquid.At 1A/dm 2Under current density and the stirring condition, be that 10min is electroplated in substrate in electroplate liquid, form silvery white bright coating, promptly obtain gun-metal with the copper sheet.
Embodiment 5
The 36g potassium pyrophosphate is dissolved in the 100mL deionized water, under condition of stirring, adds the tin protochloride of 1g and the copper sulfate of 0.8g respectively.Add additive, wherein contain epoxy chlorine alkane 0.65g/L, trolamine 0.6g/L, formaldehyde 0.7g/L, gelatin 0.06g/L; At 0.75A/dm 2Under current density and the stirring condition, be that substrate plating 8min obtains silvery white bright coating with the copper sheet.XRD result shows that coating is Cu and Cu 6Sn 5Mixture.
With the lithium sheet is negative pole, coating is anodal, used for electrolyte NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC) (1: 1: 1) ternary electrolytic solution, barrier film is Celgard 2400, in being full of the glove box of argon gas, be assembled into 2025 type button cells, then on new prestige BTS heavy-duty battery tester, carry out charge-discharge test with the charge-discharge magnification of 100mA/g.Discharging and recharging as a result show electrode has a very significantly voltage platform near 0.1V, show as Cu 6Sn 5The charging and discharging curve feature of alloy.
Embodiment 6
The 36g potassium pyrophosphate is dissolved in the 100mL distilled water, under condition of stirring, adds the tin protochloride of 3g and the copper sulfate of 0.8g respectively; Add additive, wherein contain epoxy chlorine alkane 0.75g/L, trolamine 0.55g/L, formaldehyde 0.9g/L, gelatin 0.08g/L; At 0.7A/dm 2Under current density and the stirring condition, be that substrate plating 6min obtains silvery white bright coating with the copper sheet.XRD result shows that Coating composition is mainly Cu 6Sn 5Alloy.Discharge and recharge the result and show that its voltage curve is Cu 6Sn 5The charging and discharging curve feature of alloy.
Embodiment 7
The 36g potassium pyrophosphate is dissolved in the 100mL deionized water, under condition of stirring, adds the tin protochloride of 5g and the copper sulfate of 0.8g respectively; Add additive, wherein contain epoxy chlorine alkane 0.6g/L, trolamine 0.8g/L, formaldehyde 0.65g/L, gelatin 0.05g/L; At 0.8A/dm 2Under current density and the stirring condition, be that substrate plating 8min obtains silvery white bright coating with the copper sheet.Fig. 1 has provided the XRD figure of coating, and the result shows that coating is Sn and Cu 6Sn 5The mixture of alloy.Fig. 2 is the SEM figure of coating, and coating is for covering fine and close bright coating as can be seen from Figure.Discharge and recharge the result as shown in Figure 3 and Figure 4, initial charge (embedding lithium) capacity is 434mAH/g, and still about 300mAg/h, its cycle performance obviously is better than the pure tin electrode materials through capacity after 50 all charge and discharge cycles.Fig. 5 is the coulombic efficiency that discharges and recharges of gun-metal, and coulombic efficiency is that 83%, the second week beginning efficient remains on more than 93% first as can be seen.

Claims (3)

1. the preparation method of Sn-Cu alloy material for negative pole of lithium ion cell is characterized in that its step is as follows:
1) potassium pyrophosphate is dissolved in the water, adds tin protochloride and copper sulfate more respectively, get mixing solutions, the concentration of potassium pyrophosphate is 100～400g/L, and the concentration of tin protochloride is 5～25g/L, and the concentration of copper sulfate is 3～8g/L;
2) in mixing solutions, add additive, additive is epoxy chlorine alkane, trolamine, formaldehyde and gelatin, the cumulative volume of pressing mixing solutions calculates, the content of additive in mixing solutions is epoxy chlorine alkane 0.5～1g/L, trolamine 0.5～1g/L, formaldehyde 0.50～1g/L, gelatin 0.02～0.10g/L gets electroplate liquid;
3) be that the silvery white bright coating of formation is electroplated in substrate with the copper sheet in electroplate liquid, promptly obtain gun-metal.
2. the preparation method of Sn-Cu alloy material for negative pole of lithium ion cell as claimed in claim 1 is characterized in that in step 3), and the cathode current density in the described electroplate liquid is 0.5～1A/dm 2
3. the preparation method of Sn-Cu alloy material for negative pole of lithium ion cell as claimed in claim 1 is characterized in that in step 3), and the described galvanized time is 1～10min.
CNB2006101113159A 2006-08-21 2006-08-21 preparation process of Sn-Cu alloy material for negative pole of lithium ion cell Expired - Fee Related CN100526516C (en)

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CN101969124B (en) * 2010-10-30 2013-03-13 湘潭大学 Tin-copper alloy cathode material used for lithium ion battery and preparation method thereof
CN102220610B (en) * 2011-07-29 2012-12-05 福州大学 Non-cyanide copper-tin alloy plating solution
CN103094524B (en) * 2012-12-31 2015-10-07 浙江工业大学 A kind of tin alloy membrane electrode and application thereof
CN103606659A (en) * 2013-11-15 2014-02-26 江苏天鹏电源有限公司 Lithium ion battery for gardening tool
CN104393237B (en) * 2014-09-30 2017-05-10 河南师范大学 Stannum-base alloy negative plate for lithium ion battery and preparation method thereof
CN104409707B (en) * 2014-10-15 2017-06-20 河南师范大学 A kind of kamash alloy fexible film electrode and preparation method thereof
CN105679997A (en) * 2016-01-27 2016-06-15 柳州豪祥特科技有限公司 Method for manufacturing tin-copper alloy pole piece through electrolytic process
CN105680003A (en) * 2016-01-27 2016-06-15 柳州豪祥特科技有限公司 Method for preparing tin copper alloy pole piece
CN108598361A (en) * 2018-05-17 2018-09-28 河南电池研究院有限公司 A kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery
CN112030036B (en) * 2020-09-14 2021-11-09 鹰潭盛发铜业有限公司 Tin-copper alloy and preparation method thereof
CN114032532B (en) * 2021-10-19 2023-06-16 南方科技大学 Sodium metal battery current collector and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN86105646B (en) * 1986-07-29 1988-07-20 傅熙仁 Electrolyte for bronze (copper-tin alloy) electroplating without cyanide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86105646B (en) * 1986-07-29 1988-07-20 傅熙仁 Electrolyte for bronze (copper-tin alloy) electroplating without cyanide

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