CN103326005B - Sn-Ni-Zn ternary alloy soft porous material applied to negative electrode of lithium ion battery and preparation method of Sn-Ni-Zn ternary alloy soft porous material - Google Patents
Sn-Ni-Zn ternary alloy soft porous material applied to negative electrode of lithium ion battery and preparation method of Sn-Ni-Zn ternary alloy soft porous material Download PDFInfo
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Abstract
The invention discloses a Sn-Ni-Zn ternary alloy soft porous material applied to the negative electrode of a lithium ion battery and a preparation method of the Sn-Ni-Zn ternary alloy soft porous material. The preparation method comprises the following steps of: preparing a Sn-Ni-Zn ternary alloy coating film with certain components through controlling electro-deposition conditions by an electro-deposition method, wherein an environment-friendly citrate system is taken as electroplate liquid and a soft porous conductive material is taken as a current collector; and selectively corroding the Sn-Ni-Zn ternary alloy coating film by a multifunctional composite corrosive medium to obtain the Sn-Ni-Zn ternary alloy porous negative material. Compared with the prior art, the preparation method disclosed by the invention is novel, low in cost and simple in preparation process. The obtained Sn-Ni-Zn ternary alloy soft porous material is simultaneously provided with three-dimensional through holes and semi-through holes with the apertures ranging from nanometer to micrometer and has the charging/discharging efficiency close to 100% within charging/discharging circulation; compared with a planar Sn-Ni binary alloy with the same components, the Sn-Ni-Zn ternary alloy soft porous material is greatly improved in cycling stability.
Description
Technical field
The present invention relates to a kind of technical field of lithium ion, particularly a kind of tin nickel zinc ternary alloy software porous material being applied to lithium ion battery negative and preparation method thereof.
Background technology
Lithium ion battery is a kind of rechargeable battery, and it mainly relies on lithium ion to shift work between a positive electrode and a negative electrode, is the representative of modern high performance secondary cell.Lithium ion battery has that voltage is high, specific energy is large, have extended cycle life, security performance is good, self discharge is little, can fast charging and discharging, operating temperature range advantages of higher.Chargeable lithium ion battery is most widely used power supply in the modern number code products such as current mobile phone, notebook computer, in the application of electric automobile, field of hybrid electric vehicles just at test spread.
Lithium ion battery is made up of electrode material, electrolyte, selective barrier film etc., and wherein electrode material plays decisive role to its performance.At present, negative material is graphite mainly, it have operating voltage high and steadily, abundance, the outstanding advantage such as cheap, but graphite specific capacity is low, lithium strong to solvent selectivity spreads comparatively slow in graphite, greatly limit the use of graphite.Kamash alloy has the specific capacity of about 3 times, graphite, and electrodeposition technology is simple, and cost is low, but in alloy, metallic tin content is higher, and bulk effect is more serious, causes the lost of life of battery.The approach of head it off mainly contains two, one is metallic tin and another inert metal, as copper, nickel, cobalt etc. form binary or multicomponent alloy, inert metal plays skeleton function, another approach is the porous process of alloy electrode material, especially nanometer process, can alleviate the efflorescence in kamash alloy material charge and discharge process greatly, improves efficiency for charge-discharge and the cycle life of electrode material.
Summary of the invention
In order to the deficiency for current kamash alloy lithium ion battery negative material, the invention provides a kind of tin nickel zinc ternary alloy software porous material being applied to lithium ion battery negative and preparation method thereof.
In order to realize foregoing invention object, the invention provides a kind of preparation method being applied to the tin nickel zinc ternary alloy software porous material of lithium ion battery negative, with environment-friendly type citrate system for electroplate liquid, conductive copper cloth or conductive nickel cloth is selected to be collector as porous, electrically conductive soft material, reduce costs, without the need to pore-creating process, just there is good pore structure, pass through electro-deposition, control the tin nickel zinc ternary alloy plated film with tin nickel zinc three kinds of elements that electrodeposition condition prepares definite composition, there is better structure, adopt the gentle multi-functional compound corrosive medium of performance, selective corrosion is carried out to tin nickel zinc ternary alloy plated film, because in tin nickel zinc ternary alloy, the electrode potential of Zn-ef ficiency is lower, easily be corroded, thus through selective corrosion, ensure tin nickel zinc ternary alloy rete good combination power on a current collector simultaneously, obtain tin nickel zinc ternary alloy software porous material, there is better loose structure.
The described preparation method being applied to the tin nickel zinc ternary alloy software porous material of lithium ion battery negative, comprises the following steps:
1) using porous, electrically conductive soft material as collector, surface active pretreatment is carried out to collector;
2) with environment-friendly type citrate system for electroplate liquid, the porous, electrically conductive soft material after step 1) process carries out electro-deposition, control electrodeposition condition, obtain the tin nickel zinc ternary alloy plated film of definite composition;
3) by step 2) the tin nickel zinc ternary alloy plated film of definite composition that obtains immerses in multi-functional compound corrosive medium, carries out selective corrosion;
4) the tin nickel zinc ternary alloy plated film after step 3) selective corrosion is carried out deionization washing, obtain tin nickel zinc ternary alloy software porous material.
The surface active pretreating process that described step 1) adopts is degreasing, activation one-step method, and the treatment fluid used mainly consists of: sulfuric acid (mass fraction concentration is 98%) 20-30mL/L, fatty alcohol-ether sodium sulfate (RO (CH
2cH
2o) n-SO
3na, n=2-3) 1-2mL/L, process 15-30min under normal temperature, normal temperature is about 25 DEG C.
The porous, electrically conductive soft material collector that described step 1) uses is conductive copper cloth, conductive nickel cloth etc., if conductive nickel cloth, the pore diameter range of conductive nickel cloth square hole crisscross before plating is 4-72 μm, and average pore size is 28 μm; If conductive copper cloth, the aperture of conductive copper cloth square hole crisscross before plating is 5-70 μm, and average pore size scope is 30 μm.Use conductive nickel cloth or conductive copper cloth, such material itself is loose structure, reduces costs, and without the need to carrying out porous process, and is easy to attachment.
Described step 2) electrodeposition condition that adopts is: current density is 1-1.5A/dm2, and electro-deposition 20-40min under room temperature, room temperature is about 25 DEG C.
Described step 2) electroplate liquid that adopts is environment-friendly type citrate system electroplate liquid, consists of: SnSO
48-12 g/L, NiSO
46H
2o 10-20 g/L, ZnSO
47H
2o 60-75 g/L, C
6h
5na
3o
72H
2o 80-120 g/L, C
4h
6o
610-25 g/L, KCl 5-10 g/L, PH=6.5-7.5.
Through described step 1), described step 2), obtain tin nickel zinc ternary alloy coating film thickness be 5-30 μm, mass fraction consists of: zinc 10%-60%, nickel 13%-30%, tin 20%-70%.
The multi-functional compound corrosive medium that described step 3) adopts consists of: glacial acetic acid 30-50mL/L, peregal 0.1-0.3mL/L, ammonium chloride 5-15 g/L, selective corrosion 10-60min under normal temperature.Due to the tin nickel zinc ternary alloy plated film obtained, have tin nickel zinc three kinds of elements, itself has better structural advantage than tinbase two alloy.In this kind of tin nickel zinc ternary alloy plated film, the electrode potential of Zn-ef ficiency is lower, and utilize Zn-ef ficiency electrode potential lower, nickel, tin is metastable feature in weak acid medium, adopt the multi-functional compound corrosive medium that performance is gentle, have comprehensive function, utilize the faintly acid of acetic acid, Cl
-to the moistened surface effect of the complexing of zinc ion and good penetration capacity, peregal, under normal temperature, selective corrosion is carried out to Zn-ef ficiency wherein, ensure tin nickel zinc ternary alloy rete good combination power on a current collector simultaneously.On the basis of loose structure keeping conductive copper cloth or conductive nickel cloth, realize the porous process of alloy further, there is loose structure more fully, when making as negative material, efficiency for charge-discharge can be improved further, there is higher cyclical stability.
The deionization electrical conductivity of water that described step 4) adopts is 0-10 μ s/cm.
The present invention is via above-mentioned steps 1)-4) the tin nickel zinc ternary alloy software porous material being applied to lithium ion battery negative that obtains of preparation, have aperture in half through hole, the aperture of 0.1 μm-1 μm be 3.42-41.67 μm crisscross interfibrous square opening and in the same way Inter-fiber voids be the three-dimensional through hole of 110-450nm.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is: utilize electrodeposition process to prepare tin nickel zinc ternary alloy plated film on the porous, electrically conductive soft materials such as conductive copper cloth, conductive nickel cloth, and have three-dimensional through hole and half through hole, the porous negative material of aperture from nanometer to micron concurrently with the acquisition of selective corrosion method, compared with prior art, preparation method is novel, cost is low, preparation technology is simple.In the tin nickel zinc ternary alloy software porous material charge and discharge cycles prepared, efficiency for charge-discharge is close to 100%, and compared with the plane tin nickel bianry alloy of same composition, cyclical stability increases substantially, and efficiency for charge-discharge is at 98-105%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the conductive nickel cloth before plating;
Fig. 2 is the SEM figure of tin nickel zinc ternary alloy software porous material;
Fig. 3 is the charge and discharge cycles curve map of tin nickel zinc ternary alloy software porous material;
Detailed description of the invention
Below in conjunction with the further the present invention of embodiment, but embodiment does not limit in any form the present invention.
Embodiment 1
1) using porous, electrically conductive soft material as collector, surface active pretreatment is carried out to collector.
Select conductive nickel cloth to be collector, the pore diameter range of conductive nickel cloth square hole crisscross before plating is 4-72 μm, and average pore size is 28 μm, and structure SEM is shown in Fig. 1.Conductive nickel cloth is carried out surface active pretreating process, namely carries out degreasing, activation simultaneously.The treatment fluid used mainly consists of: sulfuric acid (mass fraction concentration is 98%) 20-30mL/L, fatty alcohol-ether sodium sulfate (RO (CH
2cH
2o) n-SO
3na, n=2-3) 1-2mL/L, process 30min under normal temperature, normal temperature is about 25 DEG C.
2) with environment-friendly type citrate system for electroplate liquid, the porous, electrically conductive soft material conductive nickel cloth after step 1) process carries out electro-deposition, control electrodeposition condition, obtain the tin nickel zinc ternary alloy plated film of definite composition.
Consisting of of environment-friendly type citrate system electroplate liquid: SnSO
48 g/L, NiSO
46H
2o 10 g/L, ZnSO
47H
2o 70g/L, C
6h
5na
3o
72H
2o 80 g/L, C
4h
6o
620g/L, KCl 10g/L, PH=7.5.Electrodeposition condition is chosen as: current density is 1.5A/dm2, electro-deposition 30min under room temperature.Room temperature is about 25 DEG C.Through controlling electrodeposition condition, obtain tin nickel zinc ternary alloy plated film, thickness is 15 μm, and mass fraction consists of: zinc 29%, nickel 21%, tin 50%.
3) by step 2) the tin nickel zinc ternary alloy plated film of definite composition that obtains immerses in multi-functional compound corrosive medium, carries out selective corrosion.
Through step 2) the tin nickel zinc ternary alloy plated film that obtains, thickness is 15 μm, and mass fraction consists of: zinc 29%, nickel 21%, tin 50%, invades in Multifunctional corrosion medium and carries out selective corrosion.Selected Multifunctional corrosion medium is: glacial acetic acid 40mL/L, peregal 0.3mL/L, ammonium chloride 15g/L, selective corrosion 30min under normal temperature.
4) the tin nickel zinc ternary alloy plated film after step 3) selective corrosion carries out deionization washing, obtains tin nickel zinc ternary alloy software porous material.
Tin nickel zinc ternary alloy plated film after selective corrosion is carried out deionization washing, deionized water (0-10 μ s/cm) is adopted to wash away Multifunctional corrosion medium, then obtain tin nickel zinc ternary alloy software porous material, have aperture in half through hole, the aperture of 0.1 μm-1 μm be 3.42-41.67 μm crisscross interfibrous square opening and in the same way Inter-fiber voids be the three-dimensional through hole of 110-450nm.
Fig. 2 is shown in the SEM structural representation of the tin nickel zinc ternary alloy software porous material obtained, and by test, see the charge and discharge cycles curve diagram H curve of Fig. 3, in 14 charge and discharge cycles, its specific discharge capacity remains within the scope of 600mAh/g-400.mAh/g, efficiency for charge-discharge is close to 100%, and compared with the plane tin nickel bianry alloy of same composition, cyclical stability increases substantially.
Embodiment 2
1) using porous, electrically conductive soft material as collector, surface active pretreatment is carried out to collector.
Select conductive nickel cloth to be collector, the pore diameter range of conductive nickel cloth square hole crisscross before plating is 4-72 μm, and average pore size is 28 μm, and structure SEM is shown in Fig. 1.Conductive nickel cloth is carried out surface active pretreating process, namely carries out degreasing, activation simultaneously.The treatment fluid used mainly consists of sulfuric acid (mass fraction concentration is 98%) 20-30mL/L, fatty alcohol-ether sodium sulfate (RO (CH
2cH
2o) n-SO
3na, n=2-3) 1-2mL/L, process 20min under normal temperature, normal temperature is about 25 DEG C.
2) with environment-friendly type citrate system for electroplate liquid, the porous, electrically conductive soft material conductive nickel cloth after step 1) process carries out electro-deposition, control electrodeposition condition, obtain the tin nickel zinc ternary alloy plated film of definite composition.
Consisting of of environment-friendly type citrate system electroplate liquid: SnSO
410 g/L, NiSO
46H
2o 15 g/L, ZnSO
47H
2o 65 g/L, C
6h
5na
3o
72H
2o 100 g/L, C
4h
6o
615 g/L, KCl 8 g/L, PH=7.0.It is 1A/dm2 that electrodeposition condition is chosen as current density, and electro-deposition 25min under room temperature, room temperature is about 25 DEG C.Through electro-deposition, obtain the tin nickel zinc ternary alloy plated film of definite composition, thickness is 8 μm, and mass fraction consists of: zinc 15%, nickel 22%, tin 630%.
3) by step 2) the tin nickel zinc ternary alloy plated film of definite composition that obtains immerses in multi-functional compound corrosive medium, carries out selective corrosion.
Through step 2) the tin nickel zinc ternary alloy plated film that obtains, thickness is 8 μm, and mass fraction consists of: zinc 15%, nickel 22%, tin 63%, invades in Multifunctional corrosion medium and carries out selective corrosion.Selected Multifunctional corrosion medium is: glacial acetic acid 35mL/L, peregal 0.2mL/L, ammonium chloride 10g/L, selective corrosion 20min under normal temperature.
4) the tin nickel zinc ternary alloy plated film after step 3) selective corrosion is carried out deionization washing, obtain tin nickel zinc ternary alloy software porous material.
Tin nickel zinc ternary alloy plated film after selective corrosion is carried out anhydrating washing, deionized water (0-10 μ s/cm) is adopted to wash away Multifunctional corrosion medium, then obtain tin nickel zinc ternary alloy software porous material, have aperture in half through hole, the aperture of 0.1 μm-1 μm be 3.42-41.67 μm crisscross interfibrous square opening and in the same way Inter-fiber voids be the three-dimensional through hole of 110-450nm.
Fig. 2 is shown in the SEM structural representation of the tin nickel zinc ternary alloy software porous material obtained, and by test, specific discharge capacity change is see the charge and discharge cycles curve diagram K curve of Fig. 3.
Embodiment 3
1) using porous, electrically conductive soft material as collector, carry out surface active pretreatment.
Select conductive copper cloth to be collector, the aperture of conductive copper cloth square hole crisscross before plating is 5-70 μm, and average pore size scope is 30 μm.Conductive copper cloth is carried out surface active pretreating process, namely carries out degreasing, activation simultaneously.The treatment fluid used mainly consists of: sulfuric acid (mass fraction concentration is 98%) 20-30mL/L, fatty alcohol-ether sodium sulfate (RO (CH
2cH
2o) n-SO
3na, n=2-3) 1-2mL/L, process 20min under normal temperature, normal temperature is about 25 DEG C.
2) with environment-friendly type citrate system for electroplate liquid, the porous, electrically conductive soft material conductive copper cloth after step 1) process carries out electro-deposition, control electrodeposition condition, obtain the tin nickel zinc ternary alloy plated film of definite composition.
Consisting of of environment-friendly type citrate system electroplate liquid: SnSO
412 g/L, NiSO
46H
2o 20 g/L, ZnSO
47H
2o 75g/L, C
6h
5na
3o
72H
2o 120 g/L, C
4h
6o
625 g/L, KCl 10g/L, PH=6.5.Electrodeposition condition is: current density is 1.2A/dm2, electro-deposition 40min under room temperature.Room temperature is about 25 DEG C.Through electro-deposition, obtain the tin nickel zinc ternary alloy plated film of definite composition, thickness is 25 μm, and mass fraction consists of: zinc 25%, nickel 17%, tin 58%.
3) by step 2) the tin nickel zinc ternary alloy plated film of definite composition that obtains immerses in multi-functional compound corrosive medium, carries out selective corrosion.
Through step 2) the tin nickel zinc ternary alloy plated film that obtains, thickness is 25 μm, and mass fraction consists of: zinc 25%, nickel 17%, tin 58%, immerses in Multifunctional corrosion medium and carries out selective corrosion.Selected Multifunctional corrosion medium is glacial acetic acid 50mL/L, peregal 0.1mL/L, ammonium chloride 5g/L, selective corrosion 60min under normal temperature.
4) the tin nickel zinc ternary alloy plated film after step 3) selective corrosion carries out deionization washing, obtains tin nickel zinc ternary alloy software porous material.
Tin nickel zinc ternary alloy plated film after selective corrosion is washed, deionized water (0-10 μ s/cm) is adopted to wash away Multifunctional corrosion medium, then obtain tin nickel zinc ternary alloy software porous material, have aperture in half through hole, the aperture of 0.1 μm-1 μm be 3.42-41.67 μm crisscross interfibrous square opening and in the same way Inter-fiber voids be the three-dimensional through hole of 110-450nm.
Fig. 2 is shown in the SEM structural representation of the tin nickel zinc ternary alloy software porous material obtained, and by test, specific discharge capacity is see the charge and discharge cycles curve diagram L curve of Fig. 3.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. be applied to a preparation method for the tin nickel zinc ternary alloy software porous material of lithium ion battery negative, it is characterized in that, comprise the following steps:
1) using porous, electrically conductive soft material as collector, surface active pretreatment is carried out to collector;
2) with environment-friendly type citrate system for electroplate liquid, the porous, electrically conductive soft material after step 1) process carries out electro-deposition, control electrodeposition condition, obtain tin nickel zinc ternary alloy plated film;
3) by step 2) the tin nickel zinc ternary alloy plated film that obtains immerses in multi-functional compound corrosive medium, carries out selective corrosion;
4) the tin nickel zinc ternary alloy plated film after step 3) selective corrosion carries out deionization washing, obtains tin nickel zinc ternary alloy software porous material;
The surface active pretreating process that described step 1) adopts is degreasing, activation one-step method, and the treatment fluid used mainly consists of: mass fraction concentration is the sulfuric acid 20-30mL/L of 98%, fatty alcohol-ether sodium sulfate RO (CH
2cH
2o) n-SO
3na, n=2-3,1-2mL/L, process 15-30min under normal temperature;
The porous, electrically conductive soft material collector that described step 1) uses is conductive copper cloth or conductive nickel cloth, and during for conductive nickel cloth, the pore diameter range of conductive nickel cloth square hole crisscross before plating is 4-72 μm, and average pore size is 28 μm; During for conductive copper cloth, the aperture of conductive copper cloth square hole crisscross before plating is 5-70 μm, and average pore size scope is 30 μm;
Described step 2) electrodeposition condition that adopts is: current density is 1-1.5A/dm
2, electro-deposition 20-40min under room temperature;
Described step 2) electroplate liquid that adopts is environment-friendly type citrate system electroplate liquid, consists of: SnSO
48-12 g/L, NiSO
46H
2o 10-20 g/L, ZnSO
47H
2o 60-75 g/L, C
6h
5na
3o
72H
2o 80-120 g/L, C
4h
6o
610-25 g/L, KCl 5-10 g/L, pH=6.5-7.5;
The multi-functional compound corrosive medium that described step 3) adopts consists of: glacial acetic acid 30-50mL/L, peregal 0.1-0.3mL/L, ammonium chloride 5-15 g/L, selective corrosion 10-60min under normal temperature;
Through described step 1), described step 2), the tin nickel zinc ternary alloy coating film thickness obtained is 5-30 μm, and mass fraction consists of: zinc 10%-60%, nickel 13%-30%, tin 20%-70%.
2. be applied to a tin nickel zinc ternary alloy software porous material for lithium ion battery negative, it is characterized in that, obtain via the preparation method being applied to the tin nickel zinc ternary alloy software porous material of lithium ion battery negative according to claim 1.
3. a kind of tin nickel zinc ternary alloy software porous material being applied to lithium ion battery negative according to claim 2, it is characterized in that, obtained described tin nickel zinc ternary alloy software porous material have aperture in half through hole, the aperture of 0.1 μm-1 μm be 3.42-41.67 μm crisscross interfibrous square opening and in the same way Inter-fiber voids be the three-dimensional through hole of 110-450nm.
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| CN104577076A (en) * | 2013-10-10 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Tin-based ternary alloy negative active material and preparation method thereof |
| CN105932295A (en) * | 2016-04-22 | 2016-09-07 | 清华大学深圳研究生院 | Metal lithium secondary battery and negative electrode and porous copper current collector thereof |
| CN108110258B (en) * | 2017-12-28 | 2020-07-28 | 上海应用技术大学 | Method for constructing three-dimensional structure on surface of copper foil |
| CN112510178B (en) * | 2020-11-27 | 2024-07-02 | 华北电力大学 | Three-dimensional alloy anode material and application thereof in preparation of secondary energy storage battery |
| CN112779576B (en) * | 2020-12-25 | 2022-06-21 | 南通正海磁材有限公司 | Neodymium-iron-boron magnet composite coating and preparation method thereof |
| CN114369829B (en) * | 2022-01-12 | 2022-07-08 | 浙江花园新能源股份有限公司 | Preparation process of porous copper foil, product and application thereof |
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