CN105489872A - Copper/CNTs-tin/graphite multilayered structure lithium ion battery anode material and preparation method thereof - Google Patents
Copper/CNTs-tin/graphite multilayered structure lithium ion battery anode material and preparation method thereof Download PDFInfo
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- CN105489872A CN105489872A CN201511024662.3A CN201511024662A CN105489872A CN 105489872 A CN105489872 A CN 105489872A CN 201511024662 A CN201511024662 A CN 201511024662A CN 105489872 A CN105489872 A CN 105489872A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a copper/CNTs-tin/graphite multilayered structure lithium ion battery anode material and a preparation method thereof, and belongs to the field of lithium ion battery anode materials. The preparation method comprises the following steps: taking a coarse copper foil or a porous copper foil as a substrate, after activation of the copper foil through electrolytic degreasing, firstly preparing a CNTs-tin clad layer with a pulse-jet method, then coating a layer of graphite on the CNTs-tin clad layer, and finally carrying out heat treatment at 80-150 DEG C to prepare and obtain the copper/CNTs-tin/graphite multilayered structure anode material. Compared with the prior art, the anode material has better cycle performance and higher specific capacity, CNTs in a tin layer can play a role of connecting graphite and a copper foil current collector, a reinforced concrete structure formed by the tin material also relieves the volume expansion of tin, and a Cu6Sn5 alloy can be generated by tin and copper, so that the cycle performance of the anode material can be further promoted; and therefore, the application prospect is extremely wide.
Description
Technical field
The present invention is specifically related to a kind of copper/CNTs-tin/graphite sandwich construction lithium ion battery cathode material and its preparation method, in particular to a kind of preparation method adopting tin-based material to improve commercialization graphite cathode capacity, belong to lithium ion battery negative material and preparing technical field thereof.
Background technology
Lithium ion battery has the feature that high-energy-density, high power density, security performance are good, have extended cycle life, and not containing polluters such as lead, cadmium, mercury, is a kind of ideal energy storage device.Along with the high speed development of the portable electronics such as electric tool and notebook computer of the contour electrical demand of current power automobile, it proposes more and more higher requirement to the capacity of lithium ion battery.At present the negative material of suitability for industrialized production is carbon class material, and its theoretical specific capacity is 372mAh/g, therefore, has the emphasis that the alloy materials such as the tin-based material of high-energy-density and silicon materials become current material supplier's author investigation.
The relative silicon materials of kamash alloy material, less than though capacity has, but at present inherently, its toughness is higher than silicon materials, thus cycle performance is more excellent, more can meet the requirement of lithium ion battery repeatedly cycle charge-discharge, therefore become the object received much concern in current lithium ion battery negative field.The Tin-base Binary Alloys be widely studied at present mainly contains Sn-Cu, Sn-Sb, Sn-Ni, Sn-Co etc.
But because the restriction of material nature is (during as lithium ion battery negative material, its cycle performance is no more than carbon negative pole material), the market application of tin base alloy anode material still has certain distance, main manifestations is that irreversible capacity is larger first, repeatedly in charge and discharge cycles process, because repeatedly inlaying of lithium ion makes alloy material of cathode change in volume very big with deintercalation, cycle performance is short of.In order to solve the problem, method main is at present that the preparation alloy material of cathode of nanostructure or alloy negative material carry out adulterating or carrying out compound with other materials, as mixed third phase metal, silicon materials, the material with carbon elements such as carbon nano-tube (CNTs).Carbon can stop the direct contact between tin particles, suppresses the reunion of tin particles and grows up, playing the effect of resilient coating, carry out compound tense with kamash alloy, serve very big effect to the lifting of tin base alloy anode material performance.As the people such as LeigangXue [LeigangXue, ZhenghaoFu, YuYao, TaoHuang, AishuiYu, Three-dimensionalporousSn-Cualloyanodeforlithium-ionbatt eries, ElectrochimicaActa, 55 (2010) 7310-7314], to power on tin coating at three-dimensional foam copper, make it under the multiplying power of 0.1C, after cycle-index 100 times, specific capacity also has 404mAh/g.The people such as XinghuiWang [XinghuiWang, LeimengSun, XiaonanHu, RahmatAgungSusantyoko, QingZhang, Ni-SinanosheetnetworkashighperformanceanodeforLi-ionbatt eries, JournalofPowerSources, 280 (2015) 393-396], prepare a kind of silicon structure, make it under the multiplying power of 2C, after cycle-index 1000 times, specific capacity also has 655mAh/g.
Chinese patent CN102185131A, first with bubble hydrogen template synthesis Porous Cu collector, then adopt composite electroplating kamash alloy and carbon nano-tube to be deposited on collector and obtain porous current collector/tin-base alloy/carbon nano-tube combination electrode, improve tin base alloy anode material specific capacity and cycle performance.Chinese patent CN10457075A, silicon/carbon/graphite in lithium ion batteries mesoporous carbon/tin composite negative pole material, with mesoporous silica as template, inject stannic chloride and vegetable oil, then with NaOH corrosion, 900 DEG C of pyrolysis, removing silica template, obtain graphitization mesoporous carbon/tin composite negative pole material, improve its cycle performance, make its first capacity reach 490mAh/g.Chinese patent ZL201210562912.9, a kind of carbon-Cu
6sn
5the preparation method of alloy material of cathode, by being distributed in zinc-plated and copper plating solution after carbon nano-tube and Graphene removal of impurities, then making carbon nano-tube or graphene dispersion in electrodeposited coating after plating, obtaining carbon-Cu by heat treatment
6sn
5alloy material of cathode be used as lithium ion battery negative material time, excellent in stability.
Based on this, we adopt the Copper Foil of plating very thin CNTs-Sn composite deposite to replace original copper foil material, collector is also the possessed function of a part of active material, and apply existing high cycle performance graphite cathode material thereon, obtain a kind of novel copper-tin-graphite multilayer negative pole, under the prerequisite ensureing cycle performance, improve the capacity of electrode, this electrode has very wide application prospect.
Summary of the invention
The object of the invention is for the lower situation of the specific capacity of the not enough graphite cathode simultaneously of cycle performance of existing kamash alloy, there is provided a kind of copper/CNTs-tin/graphite sandwich construction negative material and preparation method thereof, negative material prepared by the method has high connductivity, high rate capability and long circulating performance.
For solving above technical problem, the technical solution used in the present invention is:
A kind of preparation method of copper/CNTs-tin/graphite sandwich construction lithium ion battery negative material:
(1) CNTs-tin coating is electroplated: electroplate one deck CNTs-tin coating in the side of coarse Copper Foil or porous copper foil;
(2) graphite linings is coated with: on the described CNTs-tin coating of step (1), apply one deck graphite linings;
(3) heat treatment: the material obtained in step (2) is heat-treated.
The surface roughness of the described coarse Copper Foil of step (1) is 0.4 ~ 3.0 μm, and the aperture of described porous copper foil is 1 ~ 5 μm, and the thickness of coarse Copper Foil and porous copper foil is 9 ~ 40 μm.
CNTs-tin coating 0.1 ~ 1.0 μm in step (1).
Step (1) plating CNTs-tin coating adopts impulse jet electric plating method, electroplate liquid formulation and technological parameter as follows::
Impulse jet electroplating technological parameter: current density: 5 ~ 15A/dm
2;
PH value: 3 ~ 4;
Temperature: 45 ~ 55 DEG C;
Time: 5 ~ 20s.
In step (2), the thickness of graphite linings is 80 ~ 150 μm.
Graphite linings described in step (2) comprises conductive agent and binding agent mixing composition, and the mass ratio of conductive agent and binding agent is (9 ~ 12): 1; Described conductive agent is graphite, or the mixture be combined to form for one or more and graphite of expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, and the mass percent that wherein graphite accounts for conductive agent is greater than 60%.Described graphite linings is that the slurry coating mixed by conductive agent, bonding agent and organic solvent (one or more combination of styrene, perchloroethylene, trichloroethylene) forms.
Step (3) heat treated temperature is 80 ~ 150 DEG C, and be preferably 80 ~ 100 DEG C, heat treatment time is 10 ~ 24 hours, is preferably 12 ~ 18 hours.
The preparation method of copper of the present invention/CNTs-tin/graphite sandwich construction lithium ion battery negative material, comprises following process conditions and step more specifically:
(1) preliminary treatment: negative electrode, anode electrolysis oil removing, and coarse Copper Foil is activated and cleaned;
Formula and the condition of described (1) preliminary treatment employing are as follows:
1) catholyte oil removing
Degreasing fluid temperature: 45 ~ 65 DEG C;
The oil removing time: 30 ~ 60s;
Current density: 2 ~ 8A/dm
2.
2) anode electrolysis oil removing
Degreasing fluid temperature: 45 ~ 65 DEG C;
The oil removing time: 15 ~ 30s;
Current density: 2 ~ 5A/dm
2.
3) activation and cleaning
Activator is: H
2sO
4: 20 ~ 40ml/L;
Activation temperature: room temperature;
Soak time: 20 ~ 40s.
Cleaning: get coarse Copper Foil or porous copper foil cleans 3-5 time in distilled water.
(2) CNTs-tin coating is electroplated: on coarse Copper Foil or porous copper foil, prepare one deck CNTs-tin coating by the method for impulse jet, the thickness of CNTs-tin coating is 0.1 ~ 1.0 μm.
Zinc-plated formula and the condition of electrotinning employing are as follows:
Pulse plating process parameter: current density: 5 ~ 15A/dm
2;
PH value: 3 ~ 4;
Temperature: 45 ~ 55 DEG C;
Time: 5 ~ 20s.
(3) graphite is coated with: on the described CNTs-tin coating of step (2), apply one deck graphite linings, the thickness of graphite linings is 80 ~ 150 μm.
(4) heat treatment: have the coarse Copper Foil of CNTs-tin coating and graphite linings or porous copper foil to heat-treat to plating in step (3), obtain described copper/CNTs-tin/graphite sandwich construction negative material.
Preferably, the raw material of described graphite linings comprises conductive agent and binding agent further, is that the slurry coating mixed by conductive agent, bonding agent (PVDF) and organic solvent (one or more combination of styrene, perchloroethylene, trichloroethylene) forms.The mass ratio of conductive agent and binding agent is (9 ~ 12): 1.
Described conductive agent is graphite, or the mixture to be combined to form for one or more and graphite of expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, the mass percent that wherein graphite accounts for conductive agent is greater than 60%, because when volumetric properties and cycle performance up to standard, the cost of graphite is lower.
Preferably, the surface roughness of described coarse Copper Foil is 0.4 ~ 3.0 μm, and thickness is 9 ~ 40 μm.
Preferably, the aperture of described porous copper foil is 1 ~ 5 μm, and thickness is 9 ~ 40 μm.
The present invention proposes a kind of new structure, and prepare a kind of new composite negative pole material, between the graphite linings and copper foil current collector layer of conventional graphite negative material, add one deck can the CNTs-tin layers of continuous electroplating, thus make tin layers in 1000 non-chalking situations, substantially increase the capacity of graphite cathode.
The present invention has first structurally selected a kind of shaggy Copper Foil or porous copper foil, coarse Copper Foil or porous copper foil have the large advantage of specific area, larger specific area and concaveconvex structure well can cushion the volumetric expansion of tin in charge and discharge process, this structure also plays good skeleton function simultaneously, the stress that in great buffering charge and discharge process, volumetric expansion is shunk, thus improve the cycle performance of copper/CNTs-tin/graphite sandwich construction negative material.
The present invention adopts the Copper Foil of plating very thin CNTs-Sn composite deposite to replace original copper foil material, collector is also the possessed function of a part of active material, and apply existing high cycle performance graphite cathode material thereon, obtain a kind of novel copper-CNTs-tin-graphite multilayer negative pole, under the prerequisite ensureing cycle performance, improve the capacity of electrode.
CNTs-tin coating thickness controls to be 0.1 ~ 1.0 μm by the present invention.The Main Function that this CNTs-tin coating plays in whole negative pole is the effect as connecting collector and Activated Graphite while of active material, CNTs simultaneously in CNTs-tin layers can play the effect connecting graphite and copper foil current collector, and the structure forming " reinforced concrete " with tin material also alleviates the volumetric expansion of tin.The difference of CNTs-tin thickness, connection function and volumetric expansion situation also different, therefore articulamentum will be avoided excessively thin, do not play the specific capacity improving simple graphite cathode, this negative material is made to lose the meaning of its industrialization, if articulamentum is blocked up, the volumetric expansion problem of tin material just can not get rational solution, loses the value of the marketization.
In the present invention, graphite linings uniform fold CNTs-tin layers, thus strengthen the intercrystalline binding ability of tin active material, thus the possibility that active material is come off from matrix reduces.Simultaneously due to graphite and the good conductive capability of carbon nano-tube, the speed that electronics is moved in active material strengthens greatly, the rate charge-discharge excellent performance of high power capacity superelevation cycle performance CNTs-tin/graphite double-decker negative material prepared by the present invention.
Heat treated temperature and heat treatment time are limited to by the present invention: temperature is 80 ~ 150 DEG C, and heat treatment time is 10 ~ 24 hours.This is conducive to the phase counterdiffusion of atom between active material with collector.And in such a situa-tion, after heat treatment, good gun-metal Cu just can be obtained
6sn
5, heat treatment time is long, can form more Cu
3sn phase, is unfavorable for giving full play to of material circulation performance; Heat treatment time is too short, be then unfavorable for the phase counterdiffusion of atom between active material collector.Therefore, the temperature range that heat treatment of the present invention is selected is 80 ~ 150 DEG C, and time interval is 10 ~ 24 hours, and preferable temperature interval is 80 ~ 100 DEG C, and preferred time interval is 12 ~ 18 hours.
It is high that lithium ion battery negative material prepared by the present invention has charging and discharging capacity, the advantage that cycle performance is strong.Negative pole initial charge quality capacity prepared by the present invention is 480 ~ 530mAh/g.The negative pole of the copper that the present invention prepares/CNTs-tin/graphite sandwich construction, also possesses excellent cycle performance and rate charge-discharge performance simultaneously, special capacity fade only 6% ~ 10% after 1000 circulations.This is the result produced by following 3 factors: 1, coarse Copper Foil or the larger specific area of porous copper foil and concaveconvex structure, good skeleton function can be played, the volumetric expansion of tin active material can be cushioned in large space simultaneously, reduce the efflorescence of active material in charge and discharge process and come off, the cycle performance of reinforcing material.2, the conductivity that graphite material itself is good and cycle performance, substantially increase the migration rate of electronics, also plays the effect of the volumetric expansion of buffering tin material, thus make the high rate charge-discharge excellent performance of material.3, graphite linings uniform fold CNTs-tin coating, thus strengthen the intercrystalline binding ability of tin active material, thus the possibility that active material is come off from matrix reduces; Simultaneously due to the conductive capability that graphite is good, the speed that electronics is moved in active material strengthens greatly, and the rate charge-discharge of the negative material of copper prepared by the present invention/CNTs-tin/graphite sandwich construction is functional.
Compared with other inventive method, the present invention possesses following outstanding advantages:
1, coarse Copper Foil or the larger specific area of porous copper foil and concaveconvex structure has been used, improve the shortcoming that tin base alloy anode cycle performance is not good, and then improve the specific capacity of graphite cathode on market, make the tin base cathode material of height ratio capacity to apply to market; 2, production cost is lower, and preparation process is simple; 3, use continuous electroplating, and be coated with integration and prepare lithium ion battery negative material, be conducive to the suitability for industrialized production of product; 4, non-cyanide solution is used to be electroplating solution, environmentally safe.5, in continuous electroplating process, the thickness of composite deposite and active material is accurately controlled, improve the utilance of material.
Accompanying drawing explanation
Fig. 1 is the process chart of copper disclosed by the invention/CNTs-tin/graphite sandwich construction lithium ion battery negative material preparation method;
Fig. 2 is the structural representation of copper disclosed by the invention/CNTs-tin/graphite sandwich construction lithium ion battery negative material;
Fig. 3 is the scanning electron microscope (SEM) photograph of coarse Copper Foil in copper disclosed by the invention/CNTs-tin/graphite sandwich construction lithium ion battery negative material.
Embodiment
Following examples are intended to further illustrate the present invention instead of limitation of the invention.
Embodiment
Select thickness to be 15 μm, roughness is that the coarse Copper Foil of 0.4 μm is as electroplated substrates.
One, front surface preliminary treatment is plated: electrochemical degreasing, activation processing are carried out to substrate Copper Foil;
Electrolytic degreasing current density: 5A/dm
2
Degreasing fluid temperature: 55 DEG C;
The oil removing time: 30s;
After oil removing completely, put into activator and activate;
Activator is: H
2sO
4: 30ml/L;
Activation temperature: room temperature;
Soak time: 20s.
Two, impulse jet electroplating thickness is the CNTs-tin coating of 0.5 μm:
Three, rinse, dry: with distilled water, the zinc-plated Copper Foil after plating is rinsed well, then dry.
Four, graphite linings is coated with: the graphite linings that coating 100 μm is thick on coating machine.Graphite linings is that the slurry coating mixed by conductive agent, bonding agent (PVDF) and organic solvent forms.The mass ratio of conductive agent and binding agent is 10:1, and conductive agent is graphite.
Five, heat treatment: in vacuum drying chamber 80 DEG C, dry 24h.
The Alpha-StepIQ step instrument measurement that the thickness of coating mentioned in the present invention is produced by KLATencor company of the U.S. obtains.
The capacity of lithium ion battery cycle-index table that the present invention mentions is measured by BTS high accuracy battery detection system.
Produce sample by the following method, as a comparison case.
Comparative example 1
Select the same terms in embodiment, with coarse Copper Foil for base material, be directly coated with graphite linings and heat-treat, sample not carried out to the plating of CNTs-tin coating, obtain comparative example 1.
Comparative example 2
Selecting the same terms in embodiment, take smooth copper foil as base material, carries out plating CNTs-tin coating to sample, graphite coating and heat treatment.
Cycle performance is evaluated
The material of embodiment and comparative example 1 two kinds of techniques is made battery pole piece, and in glove box, dress up button cell, result is as shown in table 1:
Table 1 cycle-index and specific capacity experimental data table
Can be found out by above-mentioned evaluation, the specific capacity of copper/CNTs-tin/graphite sandwich construction negative material prepared by the embodiment of the present invention is apparently higher than the comparative example 1 only adopting graphite to be coated with, the cycle performance of copper/CNTs-tin/graphite sandwich construction negative material prepared by the embodiment of the present invention is apparently higher than the comparative example 2 adopting smooth copper foil, and this has very important meaning for the useful life and specific capacity of improving battery.
The above embodiment of the present invention is only the use that technical solution of the present invention is described; be only enumerating of technical solution of the present invention; be not limited to technical scheme of the present invention and protection range thereof, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.
Claims (10)
1. a preparation method for copper/CNTs-tin/graphite sandwich construction lithium ion battery negative material, is characterized in that:
(1) CNTs-tin coating is electroplated: electroplate one deck CNTs-tin coating in the side of coarse Copper Foil or porous copper foil;
(2) graphite linings is coated with: on the described CNTs-tin coating of step (1), apply one deck graphite linings;
(3) heat treatment: the material obtained in step (2) is heat-treated.
2. preparation method according to claim 1, it is characterized in that: the surface roughness of the described coarse Copper Foil of step (1) is 0.4 ~ 3.0 μm, the aperture of described porous copper foil is 1 ~ 5 μm, and the thickness of coarse Copper Foil and porous copper foil is 9 ~ 40 μm.
3. preparation method according to claim 1, is characterized in that: CNTs-tin coating 0.1 ~ 1.0 μm in step (1).
4. preparation method according to claim 1, is characterized in that: step (1) plating CNTs-tin coating adopts impulse jet electric plating method, electroplate liquid formulation and technological parameter as follows::
Impulse jet electroplating technological parameter: current density: 5 ~ 15A/dm
2;
PH value: 3 ~ 4;
Temperature: 45 ~ 55 DEG C;
Time: 5 ~ 20s.
5. preparation method according to claim 1, is characterized in that: in step (2), the thickness of graphite linings is 80 ~ 150 μm.
6. preparation method according to claim 1, is characterized in that: step (3) heat treated temperature is 80 ~ 150 DEG C, and heat treatment time is 10 ~ 24 hours.
7. preparation method according to claim 6, is characterized in that: step (3) heat treated temperature is 80 ~ 100 DEG C, and heat treatment time is 12 ~ 18 hours.
8. preparation method according to claim 1, is characterized in that: the graphite linings described in step (2) comprises conductive agent and binding agent mixing composition, and the mass ratio of conductive agent and binding agent is (9 ~ 12): 1; Described conductive agent is graphite, or the mixture be combined to form for one or more and graphite of expanded graphite, carbon nano-tube, carbon fiber, activated carbon, amorphous carbon, conductive black, and the mass percent that wherein graphite accounts for conductive agent is greater than 60%.
9. preparation method according to claim 8, is characterized in that: described graphite linings is that the slurry coating mixed by conductive agent, bonding agent and organic solvent forms.
10. the copper be prepared from by the preparation method described in any one of claim 1-9/CNTs-tin/graphite sandwich construction lithium ion battery negative material.
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| CN113991059A (en) * | 2021-11-09 | 2022-01-28 | 河南电池研究院有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
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| JP2018187622A (en) * | 2017-05-08 | 2018-11-29 | ツィンファ ユニバーシティ | Manufacturing method of three-dimensional porous composite material |
| CN108206285A (en) * | 2017-12-12 | 2018-06-26 | 中国科学院物理研究所 | A kind of nanometer tin negative pole material of compound coating and its preparation method and application |
| CN110965085A (en) * | 2019-12-30 | 2020-04-07 | 中国科学院青海盐湖研究所 | Graphite composite copper foil and preparation method thereof |
| CN110965085B (en) * | 2019-12-30 | 2021-10-12 | 中国科学院青海盐湖研究所 | Graphite composite copper foil and preparation method thereof |
| CN112151757A (en) * | 2020-09-22 | 2020-12-29 | 浙江锋锂新能源科技有限公司 | Negative plate with multilayer film structure and mixed solid-liquid electrolyte lithium storage battery thereof |
| CN113991059A (en) * | 2021-11-09 | 2022-01-28 | 河南电池研究院有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
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