CN103066256B - A kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery - Google Patents

A kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery Download PDF

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CN103066256B
CN103066256B CN201310000887.XA CN201310000887A CN103066256B CN 103066256 B CN103066256 B CN 103066256B CN 201310000887 A CN201310000887 A CN 201310000887A CN 103066256 B CN103066256 B CN 103066256B
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tin
copper
nickel alloy
negative
nanometer copper
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CN103066256A (en
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袁希梅
褚道葆
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ANBAIRUI HEBEI ENERGY TECHNOLOGY Co.,Ltd.
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WUHU HUAXINNUO ELECTROCHEMICAL TECHNOLOGY Co Ltd
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery.Preparation method comprises preparation copper electroplating liquid, electro-deposition Nanometer Copper, preparation tin-nickel electrolytic plating liquid, electro-deposition tin nickel, cuts sheet by after the copper foil clean dry after plating, the lithium ion battery adopting Nanometer Copper-tin nickel alloy negative material of the present invention to prepare avoids the bulk effect of tin-nickel alloy when doff lithium, prevent the reunion of bulk tin in de-lithium process, improve the charge-discharge performance of battery, there is good cycle performance and stability, preparation method's technique of the present invention is simple, easy and simple to handle, for suitability for industrialized production provides condition.

Description

A kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery
Technical field
The present invention relates to field of lithium ion battery, particularly a kind of preparation method, Nanometer Copper-tin nickel alloy negative material, lithium ion battery of Nanometer Copper-tin nickel alloy negative material.
Background technology
Lithium ion battery has that output voltage is high, specific capacity is large, discharging voltage balance and the advantage such as fail safe is good, become one of focus of novel secondary field of chemical power source research and development, the improvement of its performance depends on the raising of anode and cathode active materials performance.At present, the negative material mainly graphite type material of commercial applications, there is the shortcomings such as first charge-discharge efficiency is low, organic solvent embeds altogether in its theoretical specific capacity relatively low (372 mAh/g) simultaneously.Along with the increase to high-capacity lithium ion cell demand, find and the high-capacity cathode material of material with carbon element can be replaced to have become one of focus of current high energy lithium ion cell research.
Metallic tin can form Li with lithium 22sn 5alloy, its theoretical specific capacity can reach 993 mAh/g, far above graphite type material, and there is not the common embedding of solvent in the charge and discharge process of this alloy material, the delamination phenomenon of similar graphite material can not occur, friendly to solvent selectivity.Therefore, tin base cathode material is subject to extensive concern in Study on Li-ion batteries field.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery.The lithium ion battery adopting Nanometer Copper-tin nickel alloy negative material of the present invention to prepare avoids the bulk effect of tin-nickel alloy when doff lithium, prevent the reunion of bulk tin in de-lithium process, improve the charge-discharge performance of battery, there is good cycle performance and stability, preparation method's technique of the present invention is simple, easy and simple to handle, for suitability for industrialized production provides condition.
The technical solution used in the present invention is:
A preparation method for Nanometer Copper-tin nickel alloy negative material, step comprises:
A, preparation copper electroplating liquid;
B, electro-deposition Nanometer Copper: add in electroplating bath by the copper electroplating liquid prepared, using inert metal sheet or copper sheet as anode, be negative electrode with copper foil, electroplate;
C, preparation tin-nickel electrolytic plating liquid;
D, electro-deposition tin nickel: add in electroplating bath by the tin-nickel electrolytic plating liquid prepared, using inert metal sheet or tin sheet as anode, with the copper foil after electro-coppering in step B for negative electrode, electroplate;
E, cut the namely obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material of sheet by after the copper foil clean dry after plating.
In described steps A, plating solution formula is: CuSO 45H 2o10 ~ 180g/L, H 2sO 410 ~ 150 g/L, lauryl sodium sulfate (SDS) 40 ~ 100g/L, polyvinylpyrrolidone (PVP) 5 ~ 20g/L;
Step B Electrodeposition Conditions is: temperature of electroplating solution 10 ~ 70 DEG C, and current density is 3 ~ 6A/dm 2, electroplating time 10 ~ 60min;
In step C, plating solution formula is: SnSO 460 ~ 180g/L, NiSO 46H 2o 60 ~ 150g/L, H 2sO 450 ~ 100 g/L, citric acid 50 ~ 100g/L, sodium potassium tartrate tetrahydrate 20 ~ 100g/L;
Step D Electrodeposition Conditions is: temperature of electroplating solution 10 ~ 70 DEG C, and current density is 3 ~ 5A/dm 2, electroplating time 10 ~ 50min;
In step B, D, inert metal sheet is titanium sheet, and copper foil can carry out one-side electroplating or two-sided plating;
Copper foil drying in step e after plating adopts vacuumize, baking temperature 80 ~ 150 DEG C.
Also can use other mantoquitas in steps A, in step C, also can use other pink salts and nickel salt, the selection of other mantoquitas, pink salt and nickel salt, not affect plating with the anion introduced and be advisable.
A kind of Nanometer Copper-tin nickel alloy negative material adopting above-mentioned preparation method to prepare;
A kind of lithium ion battery adopting the Nanometer Copper-tin nickel alloy negative material of above-mentioned side's preparation method to prepare.
The preparation method of Nanometer Copper-tin nickel alloy negative material of the present invention generates Nanometer Copper in plating preparation process, effectively prevent the bulk effect of tin-nickel alloy when doff lithium to a certain extent, improves the cycle performance of electrode; Preparation method's technique of the present invention is simple, easy and simple to handle, for suitability for industrialized production provides condition, Nanometer Copper-tin nickel alloy negative material of the present invention has good cycle performance and stability, lithium ion battery, lithium battery, polymer Li-ion battery can be applied to, there is practical value and significant economic benefit widely; Use lithium ion battery prepared by Nanometer Copper-tin nickel alloy negative material, in charge and discharge cycles process, what the nickel dissociating out with aggregated form and small part nickel and tin were formed comparatively stablizes covalent bond, effectively can suppress volumetric expansion, thus improves the cycle performance of electrode material.Discharge capacity is up to 755 more than mAh/g first; Electrodeposition process directly can prepare negative material on Copper Foil, can use conductive agent and binding agent, and the coating of gained and the adhesion of matrix are better, and simple to operate, cost is low.
Accompanying drawing explanation
Fig. 1 is the SEM collection of illustrative plates of Nanometer Copper-tin nickel alloy negative material prepared by embodiment 1.
Fig. 2 is the XRD collection of illustrative plates of Nanometer Copper-tin nickel alloy negative material prepared by embodiment 1.
Fig. 3 is the specific capacity-cycle-index curve chart of the battery that the Nanometer Copper-tin nickel alloy negative material using embodiment 1 to prepare manufactures.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but working of an invention mode is not limited thereto.
Embodiment 1
45 g SDS and 6 g PVP are dissolved in a certain amount of deionized water, then by 15 gCuSO 45H 2o, 15 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using titanium sheet as anode, take copper foil as negative electrode, 10 DEG C, current density is 3.5A/dm 2condition under two-sided plating 60min;
Citric acid and 20g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 50g, then by 60 g SnSO 4, 60 g NiSO 46H 2o, 50 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, 10 DEG C, current density is 3A/dm 2condition under two-sided plating 50min;
Copper foil after plating is cleaned at temperature 100 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 12h.
By the Nanometer Copper-tin nickel alloy negative material of above-mentioned preparation in the glove box being full of argon gas, do negative pole with metal lithium sheet, with Celgard 2400 microporous polypropylene membrane, 1 mol/L LiPF 6-EC/DMC electrolyte, is assembled into CR2025 type button cell, and LAND battery test system (CT2001A type) carries out charge-discharge performance test, and charging/discharging voltage interval is 2.5 ~ 4.2V.
From figure l, the SEM collection of illustrative plates of preparation-obtained Nanometer Copper-tin nickel alloy negative material as shown in Figure 1, can find out that this lithium ion cell nano copper-tin nickel alloy negative material is nanoscale.As shown in Figure 2, this lithium ion cell nano copper-tin nickel alloy negative material is primarily of Ni as can be seen from Figure 2 for XRD collection of illustrative plates 3sn 4composition.Specific capacity-cycle-index the curve chart of the battery using Nanometer Copper-tin nickel alloy negative material to prepare is shown in Fig. 3, and discharge capacity is up to 755 mAh/g first as can be seen from Figure 3, and after 10 circulations, discharge capacity remains on 588 mAh/g.
Embodiment 2
60g SDS and 15g PVP is dissolved in a certain amount of deionized water, then by 50 g CuSO 45H 2o, 50 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using titanium sheet as anode, take copper foil as negative electrode, 20 DEG C, current density is 4A/dm 2condition under two-sided plating 25min;
Citric acid and 30g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 60g, then by 70 g SnSO 4, 70 g NiSO 46H 2o, 70 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, 20 DEG C, current density is 4A/dm 2condition under two-sided plating 25min;
Copper foil after plating is cleaned at temperature 100 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 15h.
Cell manufacturing method is with embodiment 1.
Embodiment 3
80g SDS and 20 g PVP is dissolved in a certain amount of deionized water, then by 90g CuSO 45H 2o, 70g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using titanium sheet as anode, take copper foil as negative electrode, 30 DEG C, current density is 4.5A/dm 2condition under two-sided plating 35min;
Citric acid and 20g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 50g, then by 60 g SnSO 4, 60 g NiSO 46H 2o, 50 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, 30 DEG C, current density is 4.5A/dm 2condition under two-sided plating 35min;
Copper foil after plating is cleaned at temperature 90 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 24h.
Cell manufacturing method is with embodiment 1.
Embodiment 4
90 g SDS and 18 g PVP are dissolved in a certain amount of deionized water, then by 150g CuSO 45H 2o, 120 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using copper sheet as anode, take copper foil as negative electrode, 60 DEG C, current density is 5.5A/dm 2condition under two-sided plating 10min;
Citric acid and 90g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 90g, then by 160 g SnSO 4, 140 g NiSO 46H 2o, 90 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using tin sheet as anode, to electroplate the copper foil of copper for negative electrode, 60 DEG C, current density is 4.5A/dm 2condition under two-sided plating 45min;
Copper foil after plating is cleaned at temperature 105 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 10h.
Cell manufacturing method is with embodiment 1.
Embodiment 5
80 g SDS and 15 g PVP are dissolved in a certain amount of deionized water, then by 120g CuSO 45H 2o, 100g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using titanium sheet as anode, take copper foil as negative electrode, 65 DEG C, current density is 5A/dm 2condition under two-sided plating 40min;
Citric acid and 80g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 80g, then by 140 g SnSO 4, 120 g NiSO 46H 2o, 80 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, 50 DEG C, current density is 4A/dm 2condition under two-sided plating 45min;
Copper foil after plating is cleaned at temperature 110 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 16h.
Cell manufacturing method is with embodiment 1.
Embodiment 6
70 g SDS and 12 g PVP are dissolved in a certain amount of deionized water, then by 90g CuSO 45H 2o, 80 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using titanium sheet as anode, take copper foil as negative electrode, 40 DEG C, current density is 4A/dm 2condition under one-side electroplating 30min;
Citric acid and 60g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water by 75g, then by 100 g SnSO 4, 100 g NiSO 46H 2o, 75 g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, 40 DEG C, current density is 4A/dm 2condition under to the one-side electroplating 30min electroplating copper;
Copper foil after plating is cleaned at temperature 120 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 18h.
Cell manufacturing method is with embodiment 1.
Embodiment 7
100g SDS and 17g PVP is dissolved in a certain amount of deionized water, then by 170g CuSO 45H 2o, 145g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.Adding in electroplating bath by the electroplate liquid prepared, using copper sheet as anode, take copper foil as negative electrode, 50 DEG C, current density is 3A/dm 2condition under two-sided plating 50min;
95g citric acid and 75g sodium potassium tartrate tetrahydrate are dissolved in a certain amount of deionized water, then by 170g SnSO 4, 135 g NiSO 46H2O, 85g H 2sO 4join in above-mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid prepared is added in electroplating bath, using titanium sheet as anode, to electroplate the copper foil of copper for negative electrode, at 65 DEG C, current density two-sided plating 10min under being the condition of 5A/dm2;
Copper foil after plating is cleaned at temperature 140 DEG C, cuts sheet i.e. obtained described lithium ion battery Nanometer Copper-tin nickel alloy negative material after vacuumize 8h.
Cell manufacturing method is with embodiment 1.
The battery performance test data that the Nanometer Copper that table 1 uses embodiment 1 ~ 7 to prepare-tin nickel alloy negative material manufactures, discharge capacity is the highest first for the Nanometer Copper-tin nickel alloy negative material of embodiment 1 preparation, reach 755mAh/g, after 10 circulations, specific capacity is also be up to 588mAh/g.
Discharge capacity (mAh/g) first Specific capacity (mAh/g) after 10 circulations
Embodiment 1 755 588
Embodiment 2 731 565
Embodiment 3 692 523
Embodiment 4 723 557
Embodiment 5 714 542
Embodiment 6 719 547
Embodiment 7 705 534

Claims (8)

1. a preparation method for Nanometer Copper-tin nickel alloy negative material, step comprises:
A, preparation copper electroplating liquid;
B, electro-deposition Nanometer Copper: add in electroplating bath by the copper electroplating liquid prepared, using inert metal sheet or copper sheet as anode, be negative electrode with copper foil, electroplate;
C, preparation tin-nickel electrolytic plating liquid;
D, electro-deposition tin nickel: add in electroplating bath by the tin-nickel electrolytic plating liquid prepared, using inert metal sheet or tin sheet as anode, with the copper foil after electro-coppering in step B for negative electrode, electroplate;
E, cut sheet i.e. obtained Nanometer Copper-tin nickel alloy negative material by after the copper foil clean dry after plating.
2. the preparation method of negative material as claimed in claim 1, is characterized in that: in described steps A, plating solution formula is: CuSO 45H 2o10 ~ 180g/L, H 2sO 410 ~ 150g/L, lauryl sodium sulfate (SDS) 40 ~ 100g/L, polyvinylpyrrolidone (PVP) 5 ~ 20g/L.
3. the preparation method of negative material as claimed in claim 1, it is characterized in that: described step B Electrodeposition Conditions is: temperature of electroplating solution 10 ~ 70 DEG C, current density is 3 ~ 6A/dm 2, electroplating time 10 ~ 60min.
4. the preparation method of negative material as claimed in claim 1, is characterized in that: in described step C, plating solution formula is: SnSO 460 ~ 180g/L, NiSO 46H 2o 60 ~ 150g/L, H 2sO 450 ~ 100g/L, citric acid 50 ~ 100g/L, sodium potassium tartrate tetrahydrate 20 ~ 100g/L.
5. the preparation method of negative material as claimed in claim 1, it is characterized in that: described step D Electrodeposition Conditions is: temperature of electroplating solution 10 ~ 70 DEG C, current density is 3 ~ 5A/dm 2, electroplating time 10 ~ 50min.
6. the preparation method of negative material as claimed in claim 1, is characterized in that: in described step B, D, inert metal sheet is titanium sheet.
7. Nanometer Copper-the tin nickel alloy negative material adopting preparation method described in any one of claim 1 ~ 6 to prepare.
8. the lithium ion battery adopting Nanometer Copper-tin nickel alloy negative material according to claim 7 to prepare.
CN201310000887.XA 2013-01-04 2013-01-04 A kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery Active CN103066256B (en)

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CN104087986A (en) * 2014-06-17 2014-10-08 宁国新博能电子有限公司 Electroplating solution used for electroplating surface of copper wire
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
CN108574084B (en) * 2018-05-02 2020-06-12 河南电池研究院有限公司 Preparation method of novel tin-based nanocrystalline alloy flexible film electrode

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Publication number Priority date Publication date Assignee Title
CN101093884A (en) * 2007-05-23 2007-12-26 福建师范大学 Method for preparing cathode material of tin - copper - nickel alloy in use for batteries
CN101237038A (en) * 2008-01-21 2008-08-06 华南师范大学 A tin nickel alloy negative material of lithium ion battery and its making method
CN101969124A (en) * 2010-10-30 2011-02-09 湘潭大学 Tin-copper alloy cathode material used for lithium ion battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101093884A (en) * 2007-05-23 2007-12-26 福建师范大学 Method for preparing cathode material of tin - copper - nickel alloy in use for batteries
CN101237038A (en) * 2008-01-21 2008-08-06 华南师范大学 A tin nickel alloy negative material of lithium ion battery and its making method
CN101969124A (en) * 2010-10-30 2011-02-09 湘潭大学 Tin-copper alloy cathode material used for lithium ion battery and preparation method thereof

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