CN103022449B - Carbon nano tube-Sn-M alloy cathode material and preparation method thereof - Google Patents
Carbon nano tube-Sn-M alloy cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube-Sn-M alloy cathode material and a preparation method of the carbon nano tube-Sn-M alloy cathode material. According to the invention, carbon nano tubes (CNTs) are composited into an electrode; a CNTs-Cu connection layer is added between the active material and a current collector; and the advantages of multicomponent alloy are combined, so that the circulation property of the alloy cathode is greatly improved. According to the invention, copper foil is used as a current collector (electroplate substrate) to composite and electroplate a CNTs-Cu composite coating with the thickness of 1-5 micro and a thin tin (or tin alloy) film with a thickness of 1-4 micro in sequence; and finally the CNTs-Sn-M alloy cathode material is obtained by heat treatment. The lithium ion battery alloy cathode prepared by adopting the method has a specific discharge capacity of 500-800 mAh/g for the first time, and the specific capacity is only decayed by 2-5 percent after 100 times of circulation. According to the invention, the process is simple, the performance of the prepared alloy cathode is good, and the alloy cathode is suitable for performing large-scale industrialized production.
Description
Technical field
The invention belongs to lithium ion battery and manufacture field, relate to a kind of lithium ion battery cathode material and its preparation method, particularly relate to the negative material and preparation method thereof that a kind of CNTs-Cu of employing articulamentum connects the kamash alloy of active material and collector.
Background technology
Lithium ion battery has the feature that high-energy-density, high power density, security performance are good, have extended cycle life, and does not contain the polluters such as lead, cadmium, mercury, is a kind of comparatively desirable energy storage device.Along with the high speed development of the portable electronics such as the electric tool of the contour electric weight demand of current electric automobile and notebook computer, its capacity to lithium ion battery has proposed more and more higher requirement.The lithium ion battery negative material of suitability for industrialized production is carbon class material at present, its theoretical specific capacity is 372mAh/g, therefore, there is the emphasis that the alloy materials such as tin (Sn:994mAh/g) sill of high-energy-density and silicon materials become current material supplier author's research.
The relative silicon materials of kamash alloy material, though capacity has can't be obtained, but at present from essence, its toughness is higher than silicon materials, thereby cycle performance is more good, more can meet the repeatedly requirement of cycle charge-discharge of lithium ion battery, therefore become the object receiving much concern in current lithium ion battery negative field.The Tin-base Binary Alloys being widely studied at present mainly contains Sn-Cu, Sn-Sb, Sn-Ni, Sn-Co etc.
But because the restriction of tin-based 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 for irreversible capacity is larger first, repeatedly in charge and discharge cycles process, because repeatedly inlaying with de-embedding of lithium ion makes alloy material of cathode change in volume very big, cause tin-based material powder of detached, make cycle performance shortcoming.In order to address the above problem, at present main method is the alloy material of cathode of preparation nanostructure or alloy negative material adulterates or carry out compoundly with other materials, as mixes the material with carbon elements such as third phase metal, silicon materials, carbon nano-tube (CNTs).CNTs has good mechanical property and good conductivity, carries out compound tense with kamash alloy, and the lifting of tin base alloy anode material performance has been played to very big effect.As the people such as L.Bazin [L.Bazin, S.Mitra, P.L.Taberna, et.al.High rate capability pure Sn-based nano-architectured electrode assembly for rechargeable lithium batteries.Journal of Power Sources.188 (2009) 578 – 582] take Arrays of Copper Nanowires structure as collector, method by electro-deposition has been prepared tin base cathode material, after 500 charge and discharge cycles, its capacity is stabilized in 0.02mAh/cm always
2.People [the Yong Wang such as Yong Wang, Minghong Wu, Zheng Jiao, et.al.Sn@CNT and Sn@C@CNT nanostructures for superior reversible lithium ion storage.Chem.Mater.2009,21,3210 – 3215] to take dexterously carbon nano-tube (CNTs) be template, by chemical vapour deposition technique, prepared the tin base cathode material being wrapped up by CNTs, while being assembled into lithium ion battery, this material list has revealed very good performance, after 80 charge and discharge cycles, its specific capacity still can maintain 526mAh/g.
Chinese patent CN10206432A modifies the effective polyelectrolyte of multi-wall carbon nano-tube; and be distributed in the diethylene glycol solution of sodium borohydride; then under argon shield and condition of heating and stirring; the diethylene glycol solution of stannic chloride and cobalt chloride is added and mixed, then reaction obtains being attached with the multi-walled carbon nano-tubes negative material of tin-cobalt alloy nano particle.During as lithium ion battery negative material, irreversible capacity is little, and excellent in stability.Chinese patent CN102185131A is first with bubble hydrogen template synthesis Porous Cu collector, then adopt composite electroplating that kamash alloy and carbon nano-tube are deposited on collector and obtain porous current collector/tin-base alloy/carbon nano-tube combination electrode, improved tin base alloy anode material specific capacity and cycle performance.
Although the tin base alloy anode material function admirable that these methods are prepared, is basis mainly with nanostructure, production cost is high, is difficult to realize industrialization and produces.And this class methods to improve cyclicity be basic mainly with active material layer as thin as a wafer of preparation [J.Suzuki, K.Sekine, K.Tamura, J.PowerSources158 (2006) 1401. for T.Takamura, M.Uehara], be unfavorable for the practical application of material.
And said method is difficult to solve active material powder of detached in tin base alloy anode production application process and causes the poor problem of its cycle performance.In addition, numerous documents are found in to the research process of tin base alloy anode, the cycle performance of alloy anode is not only relevant to active material self, and and active material and collector between adhesion and electronic conductivity [Noriyuki Tamura in close relations, Ryuji Ohshita, Masahisa Fujimoto, Shin Fujitani, Maruo Kamino, Ikuo Yonezu.Journal of Power Sources107 (2002) 48 – 55].
Although the research about tin base alloy anode has had part element task, apart from the industrialization of tin base alloy anode material, still have certain distance.When active material thickness is during in practical application thickness, its cycle performance is still poor, and this has seriously hindered the application of stannum alloy cathode material in lithium ion battery field.Therefore, prepare and have better cycle performance, the lithium ion battery negative material of higher capacity is very necessary.In order to improve the cycle performance of kamash alloy, and apply in the market that promotes tin base alloy anode material, the present invention proposes and take copper strips as collector (electroplated substrates), certain thickness copper-the CNTs of composite plating composite deposite successively, re-plating tin (or alloy of tin) film, then heat treatment obtains copper-CNTs-tin (M) alloy anode.
Summary of the invention
The present invention is directed to the not good problem of alloy material of cathode cycle performance, carbon nano-tube is compound in the middle of electrode, and increased CNTs-Cu articulamentum between active material (carbon nano-tube-Xi obtaining after final step heat treatment-M composite bed) and collector, and combine the advantage of multicomponent alloy, a kind of CNTs-Sn-M alloy anode and preparation method thereof is provided.The alloy material of cathode specific discharge capacity that adopts the method to prepare is high, stable cycle performance, and be suitable for suitability for industrialized production.
A preparation method for carbon nano-tube-Sn-M alloy anode, in turn includes the following steps:
(1) CNTs is dispersed to copper plating solution, in plating solution, the mass content of CNTs is 1 ~ 5g/L; On Copper Foil, adopt direct current electrode position, prepared CNTs-Cu composite deposite;
(2) plating of preparation in step (1) is had to Copper Foil heat treatment under protective atmosphere of CNTs-Cu composite deposite;
(3) at tin plating solution, or tin mixes in plating solution with other metals (being M), on the Copper Foil obtaining in step (2), adopt direct current electrode position to prepare tin or tin alloy coat, last heat treatment obtains the CNTs-Sn-M multilayer alloy material of cathode being connected by CNTs-Cu transition zone again.
The CNTs specification adopting is: external diameter is 10 ~ 120nm, and length is 1 ~ 10 μ m.
The thickness that step (1) composite plating obtains CNTs-Cu composite deposite is 1 ~ 5 μ m.
The tin that step (2) is electroplated or the thickness of tin alloy coat are 1 ~ 4 μ m.
During step (2) heat treatment, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 200 ~ 300 ℃, and heat treatment time is 12 ~ 24 hours.
During step (3) heat treatment, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 150 ~ 300 ℃, and heat treatment time is 10 ~ 24 hours.
The metal of M representative is one or more in copper, antimony, nickel and cobalt.
A CNTs-Sn-M alloy material of cathode is the alloy material of cathode being prepared from by above-mentioned method.
Preparation method of the present invention, further comprises the steps:
(1) CNTs is carried out to removal of impurities and dispersion treatment: the present invention selects CNTs specification to be: external diameter is 10～120nm, length is 1～10 μ m, and preferably external diameter is 10 ~ 20nm, and preferred length is 1 ~ 3 μ m;
The HCl solution that is 18.25% by mass concentration adds in the container that contains CNTs, obtains the pretreatment liquid that CNTs content is 0.5～4g/L;
By the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 0.5 ~ 3 hour simultaneously, and then magnetic agitation is 8～24 hours, then CNTs is separated from pretreatment liquid, finally CNTs is dried to 10 ~ 24 hours;
(2) preparation composite plating CNTs-Cu plating solution, in plating solution, the mass content of CNTs is 1 ~ 5g/L;
(3) take Copper Foil as substrate (collector), adopt the method plating CNTs-Cu coating of direct current electrode position, its thickness is 1 ~ 5 μ m, and preferred thickness is 2 ~ 4 μ m;
Formula and the condition of electroplating CNTs-Cu coating are as follows:
Cupric pyrophosphate 60 ~ 70g/L;
Potassium pyrophosphate 280 ~ 320g/L;
Sodium potassium tartrate tetrahydrate 30 ~ 40mL/L;
Sodium dihydrogen phosphate 30 ~ 40g/L;
Ammoniacal liquor 2 ~ 3ml/L;
CNTs 1~5g/L；
PH value 8.2 ~ 8.8;
30 ~ 50 ℃ of temperature;
Cathode-current density 0.5 ~ 1A/dm
2;
(4) precursor material of preparation in step (3) is placed in to protective atmosphere heat treatment, protective atmosphere is argon gas or nitrogen or both mists.Heat treatment temperature is 200 ~ 300 ℃, and heat treatment time is 12 ~ 24 hours, and preferably temperature is 220 ~ 280 ℃, and preferably heat treatment time is 15 ~ 20 hours.
(5) adopting the copper strips with CNTs-Cu composite deposite obtaining in step (4) is substrate, adopts direct current electrode position, prepares tin or tin alloy coat, and this thickness of coating is 1 ~ 4 μ m, and preferred thickness is 2 ~ 3 μ m;
(6) precursor material of preparation in step (5) is placed in to protective atmosphere heat treatment, protective atmosphere is argon gas or nitrogen or both mists.Heat treatment temperature is 150 ~ 300 ℃, and preferably temperature is 180 ~ 240 ℃, and heat treatment time is 10 ~ 24 hours, and preferably heat treatment time is 12 ~ 18 hours, obtains the CNTs-Sn-M multilayer alloy material of cathode being connected by Cu-CNTs transition zone.
First the present invention has electroplated the cycle performance that one deck CNTs-Cu composite deposite is conducive to improve alloy anode on collector copper strips.The collector that is covered with CNTs-Cu composite deposite when plated surface is after Overheating Treatment, and the copper atom in coating and the copper atom in collector can phase counterdiffusion, greatly strengthen the adhesion between composite deposite and collector and form the complex copper coating that contains CNTs network.Meanwhile, one end of the CNTs on the top layer in composite deposite is embedded among coating, and the other end is exposed outside coating.After follow-up electrotinning or ashbury metal layer, exposed CNTs outside coating just can be covered by Sn or Sn alloy-layer originally.During heat treatment, the metallic atom in tin or ashbury metal layer spreads downwards, and formation can have the CNTs-Sn-M alloy material of cathode of CNTs network configuration.CNTs serves as skeleton in alloy anode, cushions greatly the stress that in charge and discharge process, volumetric expansion is shunk, and fundamentally improves the cycle performance of alloy anode.
It is 1 ~ 5 μ m that the present invention controls CNTs-Cu thickness of multiple plating.The Main Function that this composite deposite plays in whole CNTs-Sn-M alloy anode is to work to connect collector and active material (active material is the alloy of tin or tin) as articulamentum.Active material is different with its kind and thickness, also different to the degree of depth of articulamentum direction diffusion within a certain period of time, therefore to avoid articulamentum excessively thin, cause active material diffusion depth to surpass the articulamentum thickness that contains CNTs, make CNTs lose its connection function originally, if articulamentum is blocked up, although can not affect the performance of whole alloy anode, but can cause the waste of material, increase production cost.
The present invention adopts hydrochloric acid to process CNTs, is conducive to reduce carbon dust residual in CNTs preparation process or other impurity, and by the acid-treated CNTs structural integrity of salt, can bring into play to greatest extent himself performance.
The present invention makes restriction to heat treated temperature and heat treatment time, and this is conducive to active material and transition zone, the phase counterdiffusion of atom between transition zone and collector.And under such condition, after heat treatment, just can obtain the kamash alloy of better performances.Heat treatment time is long, can form more Cu
3sn phase, is unfavorable for giving full play to of material cycle performance.Heat treatment time is too short, is unfavorable for active material and transition zone, the phase counterdiffusion of atom between transition zone and collector.
It is high that the prepared alloy-based anode materials for Li-ion of the present invention has charging and discharging capacity, the advantage that cycle performance is strong.CNTs-Sn-M alloy anode initial charge quality capacity prepared by the present invention is 500 ~ 800mAh/g.The CNTs-Sn-M alloy material of cathode that the present invention prepares also possesses the good characteristic of cycle performance simultaneously, special capacity fade only 2% ~ 5% after 100 circulations, this is the result being produced by following 2 factors: 1, CNTs runs through between collector and active material, because CNTs itself has good conductivity and mechanical performance, can between active material and collective, play good skeleton function, reduce the efflorescence of active material in charge and discharge process and come off, the cycle performance of reinforcing material; 2, kamash alloy can carry out reversible alloy and removal alloying with lithium metal, copper metal implement is for good ductility and heat-conductivity conducting performance, when tin atom is combined formation intermetallic compound with copper atom, can in embedding and deviate from process, lithium ion play support effect for tin, the stress that when buffering lithium ion embeds, lattice variations produces, thereby make in charge and discharge process, after lithium ion repeatedly embeds, the prepared negative material of the present invention still can keep its original form;
Compare with other inventive method, the present invention possesses following outstanding advantages:
1, combine the characteristic of CNTs and alloy anode, made up the not good shortcoming of alloy anode cycle performance; 2, production cost is lower, and preparation process is simple; 3, utilization continuous electroplating, and the method for rapid thermal treatment is prepared lithium ion battery negative material, is conducive to the suitability for industrialized production of product; 4, in continuous electroplating process, the thickness of composite deposite and active material is accurately controlled, improved the utilance of material.
Related Coating composition in the present invention, by measuring with Rigaku D/MAX-RB X-ray diffraction instrument.
The capacity of lithium ion battery cycle-index table that the present invention mentions is measured by BTS high accuracy battery detection system.
Accompanying drawing explanation
Fig. 1 is that the present invention electroplates CNTs-Cu composite deposite surface topography microgram afterwards;
Fig. 2 is that the present invention electroplates Sn-Sb alloy layer surface topography microgram afterwards;
Fig. 3 is that the present invention carries out 200 ℃, the surface topography microgram after heat treatment in 24 hours to having electroplated Sn-Sb alloy layer negative material afterwards.
Embodiment:
Embodiment 1:
(1) CNTs is carried out to removal of impurities and dispersion treatment: select CNTs specification to be: external diameter is 20nm, length is 3 μ m;
The HCl solution that is 18.25% by mass concentration adds in the container that contains CNTs, obtains the pretreatment liquid that CNTs content is 4g/L;
By the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 3 hours simultaneously, and then magnetic agitation is 24 hours, then CNTs is separated from pretreatment liquid, finally CNTs is dried to 24 hours;
(2) take Copper Foil as substrate (collector), adopt direct current electrode position plating CNTs-Cu coating, its thickness is 4 μ m;
Electroplate CNTs-Cu composite deposite formula as follows with condition:
Cupric pyrophosphate 70g/L;
Potassium pyrophosphate 320g/L;
Sodium potassium tartrate tetrahydrate 40mL/L;
Sodium dihydrogen phosphate 30g/L;
Ammoniacal liquor 2ml/L;
CNTs 5g/L；
PH value 8.2;
30 ℃ of temperature;
Cathode-current density 1A/dm
2;
(3) material of preparation in step (2) is placed in to protective atmosphere heat treatment, protective atmosphere is nitrogen.Heat treatment temperature is 240 ℃, and heat treatment time is 20 hours.
(4) adopting the copper strips with CNTs-Cu composite deposite obtaining in step (3) is substrate, adopts direct current electrode position, plating tin coating, and this thickness of coating is 2 μ m;
Formula and the condition of electroplating Sn coating are as follows:
Sodium stannate 75 ~ 90g/L;
NaOH 8 ~ 12g/L;
Hydrogen peroxide 0 ~ 50g/L;
70 ~ 90 ℃ of temperature;
Cathode-current density 1 ~ 1.5A/dm
2;
(5) material of preparation in step (4) is placed in to protective atmosphere heat treatment, protective atmosphere is argon gas.Heat treatment temperature is 200 ℃, and heat treatment time is 12 hours, obtains CNTs-Sn alloy material of cathode.
Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 621mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 600mAh/g, its special capacity fade only 3%, and coulomb efficiency surpasses 96%.
Embodiment 2:
All the other steps are identical with embodiment (1).Adopt the method for codeposition at plating, to have on the Copper Foil of CNTs-Cu and electroplate the Sn-Sb alloy layer that 2 μ m are thick, last 200 ℃ of heat treatments obtain CNTs-Sn-Sb alloy anode for 24 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 603mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 585mAh/g, its special capacity fade only 2.5%, and coulomb efficiency surpasses 95%.
Embodiment 3:
All the other steps are identical with embodiment (1).Adopt the method for codeposition at plating, to have on the Copper Foil of CNTs-Cu and electroplate tin-cobalt alloy coating that 2 μ m are thick, last 200 ℃ of heat treatments obtain CNTs-Sn-Co alloy anode for 18 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 596mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 572mAh/g, its special capacity fade only 4%, and coulomb efficiency surpasses 92%.
Embodiment 4:
All the other steps are identical with embodiment (1).Adopt the method for codeposition at plating, to have on the Copper Foil of CNTs-Cu and electroplate the tin-nickel alloy layer that 2 μ m are thick, last 200 ℃ of heat treatments obtain CNTs-Sn-Ni alloy anode for 20 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 582mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 564mAh/g, its special capacity fade only 3%, and coulomb efficiency surpasses 95%.
Claims (7)
1. a preparation method for carbon nano-tube-Sn-M alloy anode, is characterized in that, in turn includes the following steps:
(1) even carbon nanotube is dispersed in copper plating solution, in plating solution, the mass content of carbon nano-tube is 1～5g/L; On Copper Foil, adopt direct current electrode position, prepared carbon nano-tube-Cu composite deposite;
(2) plating of preparation in step (1) is had to Copper Foil heat treatment under protective atmosphere of carbon nano-tube-Cu composite deposite;
(3) at tin plating solution, or tin mixes in plating solution with other metals, on the Copper Foil obtaining in step (2), adopt direct current electrode position to prepare tin or tin alloy coat, last heat treatment obtains carbon nano-tube-Sn-M multilayer alloy material of cathode that Cu-carbon nano-tube connects, and other metals are one or more in copper, antimony, nickel and cobalt; The metal of M representative is one or more in copper, antimony, nickel and cobalt.
2. according to the preparation method described in claim 1, it is characterized in that: the carbon nano-tube specification of employing is: external diameter is 10～120nm, length is 1～10 μ m.
3. according to the preparation method described in claim 1, it is characterized in that: the thickness that step (1) plating obtains carbon nano-tube-Cu composite deposite is 1～5 μ m.
4. according to the preparation method described in claim 1, it is characterized in that: in step (3), the thickness that adopts direct current electrode position to prepare tin or tin alloy coat on the Copper Foil obtaining in step (2) is 1～4 μ m.
5. preparation method according to claim 1, is characterized in that: during step (2) heat treatment, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 200～300 ℃, and heat treatment time is 12～24 hours.
6. preparation method according to claim 1, is characterized in that: during step (3) heat treatment, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 150～300 ℃, and heat treatment time is 10～24 hours.
7. carbon nano-tube-Sn-M alloy material of cathode, is characterized in that, is the alloy material of cathode being prepared from by the method described in claim 1～6 any one.
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| CN105680003A (en) * | 2016-01-27 | 2016-06-15 | 柳州豪祥特科技有限公司 | Method for preparing tin copper alloy pole piece |
| CN105679997A (en) * | 2016-01-27 | 2016-06-15 | 柳州豪祥特科技有限公司 | Method for manufacturing tin-copper alloy pole piece through electrolytic process |
| CN113224283A (en) * | 2020-08-17 | 2021-08-06 | 戴知 | Preparation method of lithium ion battery negative electrode material |
| CN112064077B (en) * | 2020-09-21 | 2021-05-14 | 江西理工大学 | Preparation method of copper foil/carbon nanotube/copper foil composite foil |
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| CN102185131A (en) * | 2011-04-13 | 2011-09-14 | 长安大学 | Preparation method of porous current collector/tin-base alloy/carbon nano-tube integrated electrode |
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