CN103022449A - 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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- CN103022449A CN103022449A CN2012105621803A CN201210562180A CN103022449A CN 103022449 A CN103022449 A CN 103022449A CN 2012105621803 A CN2012105621803 A CN 2012105621803A CN 201210562180 A CN201210562180 A CN 201210562180A CN 103022449 A CN103022449 A CN 103022449A
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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 make the 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 characteristics 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, has the emphasis that the alloy materials such as tin (Sn:994mAh/g) sill of high-energy-density and silicon materials become present 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 satisfy the repeatedly requirement of cycle charge-discharge of lithium ion battery, therefore become the object that receives much concern in the present lithium ion battery negative field.The Tin-base Binary Alloys that is widely studied at present mainly contains Sn-Cu, Sn-Sb, Sn-Ni, Sn-Co etc.
But because the restriction of tin-based material nature (during as lithium ion battery negative material, its cycle performance is no more than carbon negative pole material), the market of tin base alloy anode material is used and is still had certain distance, main manifestations is for irreversible capacity is larger first, repeatedly in the charge and discharge cycles process, because repeatedly inlaying and taking off embedding so that the alloy material of cathode change in volume is very big of lithium ion causes the tin-based material powder of detached, so that the cycle performance shortcoming.In order to address the above problem, main method is the alloy material of cathode of preparation nanostructure or the alloy negative material mixes or carry out compoundly with other materials at present, 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 very big effect has been played in the lifting of tin base alloy anode material performance.Such 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 the Arrays of Copper Nanowires structure as collector, method by electro-deposition has prepared tin base cathode material, through after 500 charge and discharge cycles, its capacity is stabilized in 0.02mAh/cm always
2People [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] dexterously take carbon nano-tube (CNTs) as template, prepared the tin base cathode material that is wrapped up by CNTs by chemical vapour deposition technique, when being assembled into lithium ion battery, this material list has revealed very good performance, after through 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 mixes, and reaction obtains being attached with the multi-walled carbon nano-tubes negative material of tin-cobalt alloy nano particle again.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 to and obtain the porous current collector/tin-base alloy/carbon nano-tube combination electrode on the collector, 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 the basis mainly with nanostructure, production cost is high, is difficult to realize industrialization production.And this class methods to improve cyclicity be basic mainly with as thin as a wafer active material layer 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 that the active material powder of detached causes the poor problem of its cycle performance in the tin base alloy anode production application process.In addition, numerous documents are found in the research process to tin base alloy anode, the cycle performance of alloy anode is not only relevant with 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 the part element task, still have certain distance apart from the industrialization of tin base alloy anode material.When active material thickness was in practical application thickness, its cycle performance was still relatively poor, and this has seriously hindered the application of stannum alloy cathode material in the 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 use in the market that promotes tin base alloy anode material, the present invention proposes take copper strips as collector (electroplated substrates), the certain thickness copper of composite plating-CNTs composite deposite successively, re-plating tin (or alloy of tin) film, heat treatment obtains copper-CNTs-tin (M) alloy anode again.
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 the electrode, and between active material (carbon nano-tube-Xi that obtains after the final step heat treatment-M composite bed) and collector, increased the CNTs-Cu articulamentum, 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.
The preparation method of a kind of carbon nano-tube-Sn-M alloy anode in turn includes the following steps:
(1) with the CNTs Uniform Dispersion to copper plating solution, the mass content of CNTs is 1 ~ 5g/L in the plating bath; Adopt direct current electrode position at Copper Foil, prepared the CNTs-Cu composite deposite;
(2) plating of preparation in the step (1) there is Copper Foil heat treatment under protective atmosphere of CNTs-Cu composite deposite;
(3) at tin plating solution, perhaps tin and other metals (being M) mixes in the plating bath, adopt direct current electrode position to prepare tin or tin alloy coat on the Copper Foil that step (2) obtains, last heat treatment obtains the CNTs-Sn-M multilayer alloy material of cathode by the connection of CNTs-Cu transition zone again.
The CNTs specification that adopts is: external diameter is 10 ~ 120nm, and length is 1 ~ 10 μ m.
The thickness that step (1) composite plating obtains the 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 the cobalt.
A kind of CNTs-Sn-M alloy material of cathode is the alloy material of cathode that is prepared from by above-mentioned method.
Preparation method of the present invention further comprises the steps:
(1) CNTs is carried out removal of impurities and dispersion treatment: the present invention selects the CNTs specification to be: external diameter is 10～120nm, and length is 1～10 μ m, and preferred external diameter is 10 ~ 20nm, and preferred length is 1 ~ 3 μ m;
Be that 18.25% HCl solution adds and contains in the container of CNTs with mass concentration, obtain the pretreatment liquid that CNTs content is 0.5～4g/L;
With the ultrasonic concussion of above-mentioned pretreatment liquid, simultaneously mechanical agitation is 0.5 ~ 3 hour, and then magnetic agitation is 8～24 hours, CNTs is separated from pretreatment liquid, at last with CNTs drying 10 ~ 24 hours again;
(2) preparation composite plating CNTs-Cu plating bath, the mass content of CNTs is 1 ~ 5g/L in the plating bath;
(3) take Copper Foil as substrate (collector), the method plating CNTs-Cu coating of employing direct current electrode position, its thickness is 1 ~ 5 μ m, preferred thickness is 2 ~ 4 μ m;
Prescription 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 with preparation in the step (3) places protective atmosphere heat treatment, and 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 preferred temperature is 220 ~ 280 ℃, and preferred heat treatment time is 15 ~ 20 hours.
(5) adopting the copper strips with the CNTs-Cu composite deposite that obtains in the step (4) is substrate, adopts direct current electrode position, preparation tin or tin alloy coat, and this thickness of coating is 1 ~ 4 μ m, preferred thickness is 2 ~ 3 μ m;
(6) precursor material with preparation in the step (5) places protective atmosphere heat treatment, and protective atmosphere is argon gas or nitrogen or both mists.Heat treatment temperature is 150 ~ 300 ℃, and preferred temperature is 180 ~ 240 ℃, and heat treatment time is 10 ~ 24 hours, and preferred heat treatment time is 12 ~ 18 hours, obtains the CNTs-Sn-M multilayer alloy material of cathode that is connected by the Cu-CNTs transition zone.
The present invention has at first electroplated the cycle performance that one deck CNTs-Cu composite deposite is conducive to improve alloy anode at the collector copper strips.The collector that is covered with the CNTs-Cu composite deposite when plated surface is after Overheating Treatment, and the copper atom in the copper atom in the coating and the collector can mutually counterdiffusion, greatly strengthens the adhesion between composite deposite and the collector and forms the complex copper coating that contains the CNTs network.Simultaneously, the end of the CNTs on the top layer in the composite deposite is embedded among the coating, and the other end exposes outside coating.After follow-up electrotinning or ashbury metal layer, the CNTs that originally exposes outside coating just can be covered by Sn or Sn alloy-layer.During heat treatment, the metallic atom in tin or the 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, cushion greatly the stress that volumetric expansion is shunk in the charge and discharge process, fundamentally improves the cycle performance of alloy anode.
The present invention is controlled to be 1 ~ 5 μ m with the 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, the degree of depth to the diffusion of articulamentum direction is also different within a certain period of time, therefore to avoid articulamentum excessively thin, cause the active material diffusion depth to surpass the articulamentum thickness that contains CNTs, so that CNTs loses its originally connection function, 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 that CNTs is processed, and is conducive to reduce carbon dust residual in the 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 the collector.And under such condition, just can obtain the kamash alloy of better performances after the heat treatment.Heat treatment time is long, can form more Cu
3The Sn phase is unfavorable for giving full play to of material cycle performance.Heat treatment time is too short, then is unfavorable for active material and transition zone, the phase counterdiffusion of atom between transition zone and the collector.
It is high that the prepared alloy-based anode materials for Li-ion of the present invention has a charging and discharging capacity, the advantage that cycle performance is strong.The CNTs-Sn-M alloy anode initial charge quality capacity of the present invention's preparation 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 who is produced by following 2 factors: 1, CNTs runs through between collector and the 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 the 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, standby good ductility and the heat-conductivity conducting performance of copper metal implement, when tin atom is combined the formation intermetallic compound with copper atom, can embed and deviate to play the support effect in the process at lithium ion for tin, the stress that lattice variations produced when the buffering lithium ion embedded, thereby so that in charge and discharge process, after lithium ion repeatedly embedded, 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, combines the characteristic of CNTs and alloy anode, remedied 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 the continuous electroplating process, the thickness of composite deposite and active material is accurately controlled, improved the utilance of material.
Related Coating composition among the present invention is 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.
Description of drawings
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 the heat treatment in 24 hours to having electroplated Sn-Sb alloy layer negative material afterwards.
Embodiment:
Embodiment 1:
(1) CNTs is carried out removal of impurities and dispersion treatment: select the CNTs specification to be: external diameter is 20nm, and length is 3 μ m;
Be that 18.25% HCl solution adds and contains in the container of CNTs with mass concentration, obtain the pretreatment liquid that CNTs content is 4g/L;
With the ultrasonic concussion of above-mentioned pretreatment liquid, simultaneously mechanical agitation is 3 hours, and then magnetic agitation is 24 hours, CNTs is separated from pretreatment liquid, at last with dry 24 hours of CNTs again;
(2) take Copper Foil as substrate (collector) adopts direct current electrode position plating CNTs-Cu coating, and its thickness is 4 μ m;
Electroplate CNTs-Cu composite deposite prescription 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 with preparation in the step (2) places protective atmosphere heat treatment, and protective atmosphere is nitrogen.Heat treatment temperature is 240 ℃, and heat treatment time is 20 hours.
(4) adopting the copper strips with the CNTs-Cu composite deposite that obtains in the step (3) is substrate, adopts direct current electrode position, the plating tin coating, and this thickness of coating is 2 μ m;
Prescription 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 with preparation in the step (4) places protective atmosphere heat treatment, and protective atmosphere is argon gas.Heat treatment temperature is 200 ℃, and heat treatment time is 12 hours, obtains the CNTs-Sn alloy material of cathode.
Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 96%.
Embodiment 2:
All the other steps are identical with embodiment (1).Adopt the method for codeposition to have the Copper Foil of CNTs-Cu to electroplate the thick Sn-Sb alloy layer of 2 μ m at plating, last 200 ℃ of heat treatments obtained the CNTs-Sn-Sb alloy anode in 24 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 95%.
Embodiment 3:
All the other steps are identical with embodiment (1).Adopt the method for codeposition to have the Copper Foil of CNTs-Cu to electroplate the thick tin of 2 μ m-cobalt alloy coating at plating, last 200 ℃ of heat treatments obtained the CNTs-Sn-Co alloy anode in 18 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 92%.
Embodiment 4:
All the other steps are identical with embodiment (1).Adopt the method for codeposition to have the Copper Foil of CNTs-Cu to electroplate the thick tin-nickel alloy layer of 2 μ m at plating, last 200 ℃ of heat treatments obtained the CNTs-Sn-Ni alloy anode in 20 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 95%.
Claims (8)
1. the preparation method of carbon nano-tube-Sn-M alloy anode is characterized in that, in turn includes the following steps:
(1) with the CNTs Uniform Dispersion to copper plating solution, the mass content of CNTs is 1 ~ 5g/L in the plating bath; Adopt direct current electrode position at Copper Foil, prepared the CNTs-Cu composite deposite;
(2) plating of preparation in the step (1) there is Copper Foil heat treatment under protective atmosphere of CNTs-Cu composite deposite;
(3) at tin plating solution, perhaps mixing in the plating bath of tin and other metals, the Copper Foil that obtains in step (2) adopts direct current electrode position to prepare tin or tin alloy coat, and last heat treatment obtains the CNTs-Sn-M multilayer alloy material of cathode that Cu-CNTs connects.
2. the preparation method described in according to claim 1, it is characterized in that: the CNTs specification of employing is: external diameter is 10 ~ 120nm, length is 1 ~ 10 μ m.
3. the preparation method described in according to claim 1, it is characterized in that: it is 1 ~ 5 μ m that step (1) is electroplated the thickness that obtains the CNTs-Cu composite deposite.
4. the preparation method described in according to claim 1, it is characterized in that: the tin that step (2) is electroplated or the thickness of tin alloy coat are 1 ~ 4m.
5. preparation method according to claim 1, it 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, it 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. preparation method according to claim 1, it is characterized in that: the metal of M representative is one or more in copper, antimony, nickel and the cobalt.
8. a CNTs-Sn-M alloy material of cathode is characterized in that, is the alloy material of cathode that is prepared from by each described method of claim 1 ~ 7.
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| CN105154938A (en) * | 2015-08-18 | 2015-12-16 | 河南天海电器有限公司 | Tin and copper carbon nanotube composite coating of automobile terminal, electroplating liquid and electroplating method for tin and copper carbon nanotube composite coating of automobile terminal |
| 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 |
| 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 |
| CN111916719A (en) * | 2020-08-17 | 2020-11-10 | 戴知 | Lithium ion battery cathode material and preparation method and application thereof |
| CN112064077A (en) * | 2020-09-21 | 2020-12-11 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105154938A (en) * | 2015-08-18 | 2015-12-16 | 河南天海电器有限公司 | Tin and copper carbon nanotube composite coating of automobile terminal, electroplating liquid and electroplating method for tin and copper carbon nanotube composite coating of automobile terminal |
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| CN112064077A (en) * | 2020-09-21 | 2020-12-11 | 江西理工大学 | Preparation method of copper foil/carbon nanotube/copper foil composite foil |
| 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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