CN103066256A - Preparation method for nanometer copper-tin nickel alloy cathode material, nanometer copper-tin nickel alloy cathode material and lithium ion battery - Google Patents
Preparation method for nanometer copper-tin nickel alloy cathode material, nanometer copper-tin nickel alloy cathode material and lithium ion battery Download PDFInfo
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- CN103066256A CN103066256A CN201310000887XA CN201310000887A CN103066256A CN 103066256 A CN103066256 A CN 103066256A CN 201310000887X A CN201310000887X A CN 201310000887XA CN 201310000887 A CN201310000887 A CN 201310000887A CN 103066256 A CN103066256 A CN 103066256A
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- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 43
- VRUVRQYVUDCDMT-UHFFFAOYSA-N [Sn].[Ni].[Cu] Chemical compound [Sn].[Ni].[Cu] VRUVRQYVUDCDMT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000010406 cathode material Substances 0.000 title abstract description 6
- 238000009713 electroplating Methods 0.000 claims abstract description 58
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011889 copper foil Substances 0.000 claims abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 23
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 241000080590 Niso Species 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 9
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009831 deintercalation Methods 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for a nanometer copper-tin nickel alloy cathode material, the nanometer copper-tin nickel alloy cathode material and a lithium ion battery. The preparation method comprises the steps as follows: preparing a copper electroplating solution; electrically depositing nanometer copper; preparing a tin nickel electroplating solution; electrically depositing tin nickel; and washing, drying and slicing an electroplated copper foil. The lithium ion battery is made by adopting the nanometer copper-tin nickel alloy cathode material, so that the volume effect of tin nickel alloy in the lithium intercalation and deintercalation processes is avoided, large tin blocks are prevented from being agglomerated in the lithium deintercalation process, the charge and discharge performance of the battery is improved, and good cycle performance and stability are obtained; and the preparation method is simple in process and easy and convenient to operate, thereby providing conditions for industrial production.
Description
Technical field
The present invention relates to the lithium ion battery field, particularly a kind of preparation method of Nanometer Copper-tin nickel alloy negative material, Nanometer Copper-tin nickel alloy negative material, lithium ion battery.
Background technology
The advantages such as lithium ion battery has that output voltage height, specific capacity are large, discharging voltage balance and fail safe are good, become one of focus of novel secondary field of chemical power source research and development, the improvement of its performance mainly depends on the raising of anode and cathode active materials performance.At present, the negative material of commercial applications mainly is graphite type material, and there are the shortcomings such as first charge-discharge efficiency is low, organic solvent embeds altogether simultaneously in its theoretical specific capacity relatively low (372 mAh/g).Along with the increase to the high-capacity lithium ion cell demand, searching can replace the high power capacity negative material of material with carbon element to 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 does not have the common embedding of solvent in the charge and discharge process of this alloy material, and the delamination phenomenon of similar graphite material can not occur, and is friendly to solvent selectivity.Therefore, tin base cathode material is subject to extensive concern in the Study on Li-ion batteries using field.
Summary of the invention
For the deficiencies in the prior art, the purpose of this invention is to provide a kind of preparation method, Nanometer Copper-tin nickel alloy negative material, lithium ion battery of Nanometer Copper-tin nickel alloy negative material.Adopt the lithium ion battery of Nanometer Copper of the present invention-tin nickel alloy negative material preparation to avoid the bulk effect of tin-nickel alloy when doff lithium, prevented from taking off the reunion of bulk tin in the lithium process, improved the charge-discharge performance of battery, has 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 kind of preparation method of Nanometer Copper-tin nickel alloy negative material, step comprises:
A, preparation copper electroplating liquid;
B, electro-deposition Nanometer Copper: the copper electroplating liquid for preparing is added in the electroplating bath,,, electroplate take copper foil as negative electrode as anode with inert metal sheet or copper sheet;
C, preparation tin-nickel electrolytic plating liquid;
D, electro-deposition tin nickel: the tin-nickel electrolytic plating liquid for preparing is added in the electroplating bath, and as anode, the copper foil in the step B after the electro-coppering is electroplated as negative electrode with inert metal sheet or tin sheet;
Cut a sheet after E, the copper foil clean dry after will electroplating and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Plating solution formula is in the described steps A: 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: 10～70 ℃ of temperature of electroplating solution, current density are 3～6A/dm
2, electroplating time 10～60min;
Plating solution formula is among the step C: 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: 10～70 ℃ of temperature of electroplating solution, current density are 3～5A/dm
2, electroplating time 10～50min;
The inert metal sheet is the titanium sheet among step B, the D, and copper foil can carry out one-side electroplating or two-sided plating;
Dry vacuumize, 80 ~ 150 ℃ of the baking temperatures of adopting of copper foil after electroplating in the step e.
Can use other mantoquitas in the steps A yet, can use other pink salts and nickel salt among the step C yet, the selection of other mantoquitas, pink salt and nickel salt does not affect plating with the anion of introducing and is advisable.
A kind of Nanometer Copper-tin nickel alloy negative material that adopts above-mentioned preparation method's preparation;
A kind of lithium ion battery that Nanometer Copper-tin nickel alloy negative material prepares that adopts above-mentioned side's preparation method.
The preparation method of Nanometer Copper-tin nickel alloy negative material of the present invention has generated Nanometer Copper in electroplating preparation process, effectively avoided to a certain extent the bulk effect of tin-nickel alloy when doff lithium, has improved 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, can be applied to lithium ion battery, lithium battery, polymer Li-ion battery, have widely practical value and significant economic benefit; Use the lithium ion battery of Nanometer Copper-tin nickel alloy negative material preparation, in the charge and discharge cycles process, with the reunion form free out nickel and small part nickel and tin form stablize covalent bond, can effectively suppress volumetric expansion, thus the cycle performance of raising electrode material.Discharge capacity is up to more than 755 mAh/g first; Electrodeposition process can directly prepare negative material at 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.
Description of drawings
Fig. 1 is the SEM collection of illustrative plates of the Nanometer Copper-tin nickel alloy negative material of embodiment 1 preparation.
Fig. 2 is the XRD collection of illustrative plates of the Nanometer Copper-tin nickel alloy negative material of embodiment 1 preparation.
Fig. 3 is the specific capacity-cycle-index curve chart of the Nanometer Copper that uses embodiment 1 preparation-battery that tin nickel alloy negative material is made.
Embodiment
The present invention will be further described below in conjunction with embodiment, but the working of an invention mode is not limited to this.
Embodiment 1
45 g SDS and 6 g PVP are dissolved in a certain amount of deionized water, then with 15 g CuSO
45H
2O, 15 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 3.5A/dm at 10 ℃, current density with the titanium sheet
2Condition under two-sided plating 60min;
50g is dissolved in citric acid and 20g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 60 g SnSO
4, 60 g NiSO
46H
2O, 50 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 3A/dm at 10 ℃, current density with the titanium sheet
2Condition under two-sided plating 50min;
Copper foil after electroplating cleaned behind 100 ℃ of lower vacuumize 12h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Nanometer Copper-the tin nickel alloy negative material of above-mentioned preparation in being full of the glove box of argon gas, is done negative pole with metal lithium sheet, with Celgard 2400 microporous polypropylene membranes, 1 mol/L LiPF
6-EC/DMC electrolyte is assembled into CR2025 type button cell, carries out the charge-discharge performance test at LAND battery test system (CT2001A type), and the charging/discharging voltage interval is 2.5 ~ 4.2V.
The SEM collection of illustrative plates of preparation-obtained Nanometer Copper-tin nickel alloy negative material can find out that from figure l this lithium ion cell nano copper-tin nickel alloy negative material is nanoscale as shown in Figure 1.The XRD collection of illustrative plates as shown in Figure 2, this lithium ion cell nano copper-tin nickel alloy negative material is mainly by Ni as can be seen from Figure 2
3Sn
4Form.The specific capacity of the battery of use Nanometer Copper-tin nickel alloy negative material preparation-cycle-index curve chart is seen Fig. 3, and discharge capacity is up to 755 mAh/g first as can be seen from Figure 3, and discharge capacity remains on 588 mAh/g after 10 circulations.
60g SDS and 15g PVP are dissolved in a certain amount of deionized water, then with 50 g CuSO
45H
2O, 50 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 4A/dm at 20 ℃, current density with the titanium sheet
2Condition under two-sided plating 25min;
60g is dissolved in citric acid and 30g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 70 g SnSO
4, 70 g NiSO
46H
2O, 70 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 4A/dm at 20 ℃, current density with the titanium sheet
2Condition under two-sided plating 25min;
Copper foil after electroplating cleaned behind 100 ℃ of lower vacuumize 15h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Cell manufacturing method is with embodiment 1.
Embodiment 3
80g SDS and 20 g PVP are dissolved in a certain amount of deionized water, then with 90g CuSO
45H
2O, 70g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 4.5A/dm at 30 ℃, current density with the titanium sheet
2Condition under two-sided plating 35min;
50g is dissolved in citric acid and 20g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 60 g SnSO
4, 60 g NiSO
46H
2O, 50 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 4.5A/dm at 30 ℃, current density with the titanium sheet
2Condition under two-sided plating 35min;
Copper foil after electroplating cleaned behind 90 ℃ of lower vacuumize 24h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
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 with 150 g CuSO
45H
2O, 120 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 5.5A/dm at 60 ℃, current density with copper sheet
2Condition under two-sided plating 10min;
90g is dissolved in citric acid and 90g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 160 g SnSO
4, 140 g NiSO
46H
2O, 90 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 4.5A/dm at 60 ℃, current density with the tin sheet
2Condition under two-sided plating 45min;
Copper foil after electroplating cleaned behind 105 ℃ of lower vacuumize 10h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
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 with 120 g CuSO
45H
2O, 100g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 5A/dm at 65 ℃, current density with the titanium sheet
2Condition under two-sided plating 40min;
80g is dissolved in citric acid and 80g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 140 g SnSO
4, 120 g NiSO
46H
2O, 80 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 4A/dm at 50 ℃, current density with the titanium sheet
2Condition under two-sided plating 45min;
Copper foil after electroplating cleaned behind 110 ℃ of lower vacuumize 16h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Cell manufacturing method is with embodiment 1.
70 g SDS and 12 g PVP are dissolved in a certain amount of deionized water, then with 90 g CuSO
45H
2O, 80 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 4A/dm at 40 ℃, current density with the titanium sheet
2Condition under one-side electroplating 30min;
75g is dissolved in citric acid and 60g sodium potassium tartrate tetrahydrate in a certain amount of deionized water, then with 100 g SnSO
4, 100 g NiSO
46H
2O, 75 g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is 4A/dm at 40 ℃, current density with the titanium sheet
2Condition under to electroplating the one-side electroplating 30min of copper;
Copper foil after electroplating cleaned behind 120 ℃ of lower vacuumize 18h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Cell manufacturing method is with embodiment 1.
Embodiment 7
100g SDS and 17g PVP are dissolved in a certain amount of deionized water, then with 170g CuSO
45H
2O, 145g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take copper foil as negative electrode, is 3A/dm at 50 ℃, current density with copper sheet
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 with 170g SnSO
4, 135 g NiSO
46H2O, 85g H
2SO
4Join in the mentioned solution and dissolve, add water and be settled to 1L.The electroplate liquid for preparing is added in the electroplating bath, as anode, take the copper foil of electroplating copper as negative electrode, is two-sided plating 10min under the condition of 5A/dm2 at 65 ℃, current density with the titanium sheet;
Copper foil after electroplating cleaned behind 140 ℃ of lower vacuumize 8h of temperature, cut a sheet and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
Cell manufacturing method is with embodiment 1.
Table 1 uses the battery performance test data that Nanometer Copper-tin nickel alloy negative material is made of embodiment 1 ~ 7 preparation, discharge capacity is the highest first for the Nanometer Copper-tin nickel alloy negative material of embodiment 1 preparation, reach 755mAh/g, specific capacity also is to be up to 588mAh/g after 10 circulations.
| Discharge capacity (mAh/g) first | Specific capacity (mAh/g) after 10 circulations | |
| Embodiment 1 | 755 | 588 |
| |
731 | 565 |
| Embodiment 3 | 692 | 523 |
| Embodiment 4 | 723 | 557 |
| Embodiment 5 | 714 | 542 |
| |
719 | 547 |
| Embodiment 7 | 705 | 534 |
Claims (8)
1. the preparation method of a Nanometer Copper-tin nickel alloy negative material, step comprises:
A, preparation copper electroplating liquid;
B, electro-deposition Nanometer Copper: the copper electroplating liquid for preparing is added in the electroplating bath,,, electroplate take copper foil as negative electrode as anode with inert metal sheet or copper sheet;
C, preparation tin-nickel electrolytic plating liquid;
D, electro-deposition tin nickel: the tin-nickel electrolytic plating liquid for preparing is added in the electroplating bath, and as anode, the copper foil in the step B after the electro-coppering is electroplated as negative electrode with inert metal sheet or tin sheet;
Cut a sheet after E, the copper foil clean dry after will electroplating and namely make described lithium ion battery with Nanometer Copper-tin nickel alloy negative material.
2. negative material as claimed in claim 1, it is characterized in that: plating solution formula is in the described steps A: CuSO
45H
2O10～180g/L, H
2SO
410～150 g/L, lauryl sodium sulfate (SDS) 40～100g/L, polyvinylpyrrolidone (PVP) 5～20g/L.
3. negative material as claimed in claim 1, it is characterized in that: described step B Electrodeposition Conditions is: 10～70 ℃ of temperature of electroplating solution, current density are 3～6A/dm
2, electroplating time 10～60min.
4. negative material as claimed in claim 1, it is characterized in that: plating solution formula is among the described step C: 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.
5. negative material as claimed in claim 1, it is characterized in that: described step D Electrodeposition Conditions is: 10～70 ℃ of temperature of electroplating solution, current density are 3～5A/dm
2, electroplating time 10～50min.
6. negative material as claimed in claim 1, it is characterized in that: the inert metal sheet is the titanium sheet among described step B, the D.
7. Nanometer Copper-tin nickel alloy negative material that adopts the described preparation method's preparation of claim 1 ~ 6.
8. lithium ion battery that adopts the preparation of Nanometer Copper-tin nickel alloy negative material.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104393237A (en) * | 2014-09-30 | 2015-03-04 | 河南师范大学 | Stannum-base alloy negative plate for lithium ion battery and preparation method thereof |
| CN108574084A (en) * | 2018-05-02 | 2018-09-25 | 河南电池研究院有限公司 | A kind of preparation method of novel tin Based Nanocrystalline Alloys fexible film electrode |
Citations (3)
| 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 |
-
2013
- 2013-01-04 CN CN201310000887.XA patent/CN103066256B/en active Active
Patent Citations (3)
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104393237A (en) * | 2014-09-30 | 2015-03-04 | 河南师范大学 | Stannum-base alloy negative plate for lithium ion battery and preparation method thereof |
| CN108574084A (en) * | 2018-05-02 | 2018-09-25 | 河南电池研究院有限公司 | A kind of preparation method of novel tin Based Nanocrystalline Alloys fexible film electrode |
| 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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| CN103066256B (en) | 2015-08-26 |
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