CN103022424A - Carbon nano tube enhanced tin-nickel alloy cathode and preparation method thereof - Google Patents
Carbon nano tube enhanced tin-nickel alloy cathode and preparation method thereof Download PDFInfo
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- CN103022424A CN103022424A CN2012105621926A CN201210562192A CN103022424A CN 103022424 A CN103022424 A CN 103022424A CN 2012105621926 A CN2012105621926 A CN 2012105621926A CN 201210562192 A CN201210562192 A CN 201210562192A CN 103022424 A CN103022424 A CN 103022424A
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Abstract
The invention discloses a carbon nano tube enhanced tin-nickel alloy cathode and a preparation method of the cathode. According to the invention, firstly, a nickel plating with the thickness of 10-500 nm is chemically plated on CNTs (carbon nano tubes); then the nickel plated CNTs are uniformly distributed in a tin plating solution; copper foil is further used as a current collector (electroplating substrate) to electroplate a thin Sn-(CNTs-Ni) film with the thickness of 0.1-3 micro; and finally, a CNTs-tin-nickel alloy cathode is obtained by heat treatment. The lithium ion battery alloy cathode prepared by adopting the method has a specific discharge capacity of 500-700 mAh/g for the first time, and the specific capacity is only decayed by 4-6 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 tin base alloy anode material that a kind of carbon nano-tube that adopts the nickel plating modification mixes and preparation method thereof.
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 preparation multicomponent alloy (comprising tin copper nickel, tin copper cobalt, tin copper antimony etc.) at present, the alloy material of cathode of nanostructure or alloy negative material mix or carry out compound with other materials, as mix the third phase metal, silicon materials, the material with carbon elements such as carbon nano-tube (CNTs).
The carbon nanomaterial superior performance, except having the nano effects such as skin effect that conventional nano material has, small-size effect, have good electrical and thermal conductivity performance toward contact, the characteristic that high intensity etc. are unique, thereby very be widely used in current field of scientific study.The carbon nanomaterial that wherein gets most of the attention mainly contains carbon nano-tube and Graphene.Carbon nano-tube is as monodimension nanometer material, and is lightweight, and hexagonal structure connects perfect, has many unusual mechanics, electricity and chemical property.Graphene is not only in the known materials the thinnest a kind of, also very firmly hard; As simple substance, it is all faster than known conductor that it at room temperature transmits the speed of electronics.Its wide application prospect of going deep into along with carbon nano-tube and nano materials research also constantly showed in recent years.
Carbon nano-tube and Graphene all have good mechanical property and good conductivity, carry 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-basednano-architectured electrode assembly for rechargeable lithium batteries.Journal ofPower 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/cm2 always.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 ionstorage.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.Chinese patent CN101207199A with carbon nanotube dispersed to having added in the middle of the composite plating bath of the sulfuric acid of additive and stannous sulfate, re-plating has obtained the tin-carbon nanometer tube combination electrode, for the pure tin electrode, its cycle performance has also obtained larger lifting.
The work that CNTs is applied to the alloy anode field has obtained certain effect, but with regard to CNTs, its surface curvature is large, difficulties in dispersion, and specification requirement is high, therefore, CNTs is carried out surface modification become more widely one of the method for CNTs application that makes.Such as improved chemical plating nickel technologies of employing such as Chen Xiaohua, and by heat treatment, obtain continuous, smooth, uniform nickel coating on the CNTs surface, greatly reduced the application threshold of CNTs.
Chemical plating is by reducing agent the redox reaction effect to occur in same solution when no current passes through (without exterior power), thereby makes the metal ion reduce deposition at the lip-deep a kind of nickel plating process of self-catalysis.Progress along with industrial expansion and scientific and technological progress, chemical nickel plating has become the very promising technology of a kind of tool, compare with other coating methods, chemical plating has following advantage: 1. can be on the part that various materials such as trip metal, semiconductor and non-conductor etc. are made metal lining; 2. no matter how complicated the geometry of part is, all places that can touch solution can both obtain the coating of even thickness, the dispersibility of chemical plating solution is excellent, be not subjected to the prophet of External Shape complexity, without significantly edge effect, therefore be particularly suitable for the plating of complex parts, pipe fitting inner wall, blind bored member; 3. process equipment is simple, need not power supply, transmission system and auxiliary electrode, and is simple to operate; 4. coating is fine and close, and hole is few; 5. adhesion is because electrodeposited coating; 6. coating often has special chemistry, mechanics or magnetic property.
Chemical nickel plating, all is widely used at nearly all industrial department with its excellent functional coating as one of field of surface treatment new technology with fastest developing speed.CNTs is carried out surface modification work has had certain basis, but with modification the CNTs work that is applied to again tin base alloy anode yet there are no report.
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.
Summary of the invention
The objective of the invention is for the not good problem of alloy material of cathode cycle performance, propose tin nickel alloy negative of a kind of carbon nano-tube enhancing and preparation method thereof.When the tin nickel alloy negative that this carbon nano-tube strengthens prepares CNTs has been carried out the chemical nickel plating processing, both improved the uniformity that CNTs distributes in the electroplating process in active material (the tin nickel that obtains after the final step heat treatment-carbon nano-tube composite bed), can make again the heat treatment afterproduct form multicomponent alloy, and combine the high strength of carbon nano-tube and the advantage of high conductivity, further improve the cycle performance of active material self.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 the tin nickel alloy negative that a kind of carbon nano-tube strengthens comprises the steps:
(1) adopt first chemical plating to CNTs plated nickel coating, then with the CNTs after the nickel plating with the concentration Uniform Dispersion of 2 ~ 8g/L to tin plating solution;
(2) take Copper Foil as substrate, adopt the composite plating bath of step (1) preparation, adopt direct current electrode position to prepare Sn-(CNTs-Ni) composite deposite;
(3) there is the Copper Foil of Sn-(CNTs-Ni) composite deposite to heat-treat to the plating that obtains in the step (2), finally obtains the tin nickel alloy negative that carbon nano-tube strengthens.
Described CNTs specification is: external diameter is 10 ~ 100nm, and length is 1 ~ 10 μ m.
The thickness of the chemical Ni-plating layer on the CNTs is 10 ~ 500nm.
The thickness of the described Sn-of step (2) (CNTs-Ni) composite deposite is 0.1 ~ 3 μ m.
During 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 3 ~ 12 hours.
The tin nickel alloy negative that a kind of carbon nano-tube strengthens is to be 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 ~ 100nm, and length is 1 ~ 10 μ m, and preferred external diameter is 10 ~ 20nm, and preferred length is 1 ~ 3 μ m;
To the CNTs treatment step be: be first 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;
Again with the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 0.5 ~ 3 hour simultaneously, and then magnetic agitation is 8 ~ 24 hours, CNTs is separated from pretreatment liquid, at last with CNTs drying 10 ~ 24 hours again;
(2) then adopting chemical plating is the nickel coating of 10 ~ 500nm to the CNTs plated thickness, then with the CNTs Uniform Dispersion after the nickel plating to tin plating solution, wherein the content of CNTs-Ni is 2 ~ 8g/L.
Prescription and the condition of chemical nickel plating are as follows:
(3) take Copper Foil as substrate, adopt the composite plating bath of step (2) preparation, adopting direct current electrode position to prepare thickness is 0.1 ~ 3 μ m Sn-(CNTs-Ni) composite deposite.
Prescription and the condition of electroplating Sn-(CNTs-Ni) are as follows:
Sodium stannate 75 ~ 90g/L;
NaOH 8 ~ 12g/L;
Hydrogen peroxide 0 ~ 50g/L;
CNTs-Ni 2~8g/L；
70 ~ 90 ℃ of temperature;
Cathode-current density 1 ~ 1.5A/dm
2
(4) to the Copper Foil of plating Sn-(CNTs-Ni) composite deposite that obtains in the step (3) 150 ~ 300 ℃ of heat treatments 3 ~ 12 hours, finally obtain the tin nickel alloy negative that CNTs strengthens.
The present invention proposes before electroplating the CNTs composite deposite CNTs to be carried out chemical plating and processes: on the one hand, with the CNTs of chemical deposit easier depositing in the middle of the tin coating in electroplating process, and improve CNTs distributing homogeneity in coating in electroplating process; On the other hand, the coating on CNTs surface can strengthen the adhesion between the CNTs and electrodeposited coating in the electroplating process, makes between CNTs and the electrodeposited coating in conjunction with tightr.
The present invention selects metallic nickel as object when chemical plating, because nickel is high conductive metal material, and there has been part report that nickel is applied in the middle of the alloy anode, form multicomponent alloy with tin, the stress of lithium ion when embedding in the buffering charge and discharge process, thereby the cycle performance of raising alloy anode.
Among the present invention, when heat treatment, the metallic atom in Sn-(CNTs-Ni) coating spreads downwards, and formation can have the CNTs-tin nickel alloy negative take CNTs as network configuration.CNTs serves as skeleton in alloy anode, cushion greatly the stress that volumetric expansion is shunk in the charge and discharge process, thereby greatly improves the cycle performance of alloy anode.
Among the present invention, CNTs can be evenly distributed on the active material portion of whole negative pole in the coating, part CNTs is through the intergranule of active material, thus the binding ability between the enhanced activity material grains, thereby so that active material reduce from the possibility that matrix comes off.Simultaneously because the good conductive capability of CNTs, so that the speed that electronics moves in active material strengthens greatly, so that the alloy anode rate charge-discharge performance of the present invention's preparation is outstanding.In addition, in charge and discharge process, the part active material still can produce be full of cracks, but because connection and the conductive channel effect of CNTs, so that this part material can be brought into play its charge-discharge performance preferably, thereby greatly promote the cycle performance of tin base alloy anode.
The specification of the CNTs that the present invention selects is external diameter 10 ~ 100nm, and length is 1 ~ 10 μ m.Select this external diameter to be because the conductive capability of CNTs is relevant with diameter, when 30nm was following, external diameter was less, and electric conductivity is better, and in conjunction with the CNTs cost, it is 10 ~ 20nm that the present invention preferentially selects the CNTs external diameter.Because the maximum ga(u)ge of Sn-(CNTs-Ni) coating is about 3 μ m among the present invention, CNTs length is long, can cause most of CNTs cross direction profiles in the middle of coating and can't make more CNTs reach the purpose that protrudes from the coating outside, so the preferred CNTs length of the present invention is 1 ~ 3 μ m.
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 prepared alloy-based anode materials for Li-ion of the present invention has the charging and discharging capacity height, the advantage that cycle performance is strong.The tin nickel alloy negative initial charge quality capacity that the CNTs of the present invention's preparation strengthens is 600 ~ 800mAh/g.The tin nickel alloy negative that the CNTs that the present invention prepares strengthens also possesses good cycle performance and rate charge-discharge performance simultaneously, special capacity fade only 4% ~ 6% after 200 circulations, under the 10C discharging condition, specific capacity still can reach 475mAh/g after its 200 times circulations.This is the result who is produced by following 2 factors: 1, CNTs runs through active material inside, for the migration of electronics provides conductive channel, has greatly improved the migration rate of electronics, thereby so that the high rate charge-discharge performance of material significantly improve; 2, the tinbase multicomponent alloy can carry out reversible alloy and removal alloying with lithium metal, standby good ductility and the heat-conductivity conducting performance of nickel metal implement, when tin atom is combined the formation intermetallic compound with nickle 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, CNTs is carried out chemical nickel plating and process, improve the uniformity that CNTs distributes in the electroplating process in active material, can make again the heat treatment afterproduct form multicomponent alloy, improve the cycle performance of active material self; 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, heat treatment temperature is lower, and the time is shorter, reduces production costs energy savings.
Related Coating composition among the present invention is by measuring with Rigaku D/MAX-RB X-ray diffraction instrument.
The surface topography of Sn-involved in the present invention (CNTs-Ni) composite deposite is measured by KYKY-2800 type scanning electron microscopy.
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 Sn-(CNTs-Ni) composite deposite surface topography microgram afterwards;
Fig. 2 is that the present invention electroplates again heat treatment surface topography microgram afterwards of Sn-(CNTs-Ni) composite deposite.
Embodiment:
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1:
(1) CNTs is carried out removal of impurities and dispersion treatment, select the CNTs specification to be: external diameter is 10 ~ 20nm, and length is 1 ~ 3 μ m;
To the CNTs treatment step be: be first that 18.25% HCl solution adds and contains in the container of CNTs with mass concentration, obtain the pretreatment liquid that CNTs content is 2g/L;
Again with the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 2 hours simultaneously, and then magnetic agitation is 8 hours, CNTs is separated from pretreatment liquid, at last with dry 24 hours of CNTs again;
(2) then adopting chemical plating is the nickel coating of 100nm to the CNTs plated thickness,
Prescription and the condition of chemical nickel plating are as follows:
(3) take Copper Foil as substrate, adopt the composite plating bath of following prescription, adopting direct current electrode position to prepare thickness is 2 μ m Sn-(CNTs-Ni) composite deposites.
Prescription and the condition of electroplating Sn-(CNTs-Ni) are as follows:
Sodium stannate 90g/L;
NaOH 12g/L;
Hydrogen peroxide 50g/L;
CNTs-Ni 8g/L；
90 ℃ of temperature;
Cathode-current density 1.5A/dm
2
(4) to the Copper Foil of plating Sn-(CNTs-Ni) composite deposite that obtains in the step (3) under 200 ℃ take nitrogen as protective atmosphere, heat treatment 6 hours finally obtains the tin nickel alloy negative that CNTs strengthens.
Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 598mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 574mAh/g, its special capacity fade only 4%, and enclosed pasture efficient surpasses 98%.
Embodiment 2:
All the other steps are identical with embodiment 1.Last 200 ℃ of heat treatments obtained the tin nickel alloy negative that CNTs strengthens in 12 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 588mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 552.7mAh/g, its special capacity fade only 6%, and enclosed pasture efficient surpasses 98%.
Embodiment 3:
All the other steps are identical with embodiment 1.Last 200 ℃ of heat treatments obtained the tin nickel alloy negative that CNTs strengthens in 3 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 594mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 564mAh/g, its special capacity fade only 5%, and enclosed pasture efficient surpasses 98%.
Claims (6)
1. the preparation method of the tin nickel alloy negative of a carbon nano-tube enhancing is characterized in that, comprises the steps:
(1) adopt first chemical plating to CNTs plated nickel coating, then with the CNTs after the nickel plating with the concentration Uniform Dispersion of 2 ~ 8g/L to tin plating solution;
(2) take Copper Foil as substrate, adopt the composite plating bath of step (1) preparation, adopt direct current electrode position, preparation Sn-(CNTs-Ni) composite deposite;
(3) there is the Copper Foil of Sn-(CNTs-Ni) composite deposite to heat-treat to the plating that obtains in the step (2), finally obtains the tin nickel alloy negative that carbon nano-tube strengthens.
2. the preparation method of the tin nickel alloy negative that strengthens of carbon nano-tube according to claim 1, it is characterized in that: described CNTs specification is: external diameter is 10 ~ 100nm, length is 1 ~ 10 μ m.
3. the preparation method of the tin nickel alloy negative of carbon nano-tube enhancing according to claim 1 is characterized in that the thickness of the chemical Ni-plating layer on the CNTs is 10 ~ 500nm.
4. the preparation method of the tin nickel alloy negative that strengthens of carbon nano-tube according to claim 1, it is characterized in that: the thickness of the described Sn-of step (2) (CNTs-Ni) composite deposite is 0.1 ~ 3 μ m.
5. the preparation method of the tin nickel alloy negative that strengthens of carbon nano-tube according to claim 1; it is characterized in that: during heat treatment; the protective atmosphere that adopts is argon gas or nitrogen or both mists, and heat treatment temperature is 150 ~ 300 ℃, and heat treatment time is 3 ~ 12 hours.
6. the tin nickel alloy negative that carbon nano-tube strengthens is characterized in that, is the tin nickel alloy negative that is strengthened by the carbon nano-tube that the described method of claim 1 ~ 5 any one is prepared from.
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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 |
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| CN102136567A (en) * | 2011-02-14 | 2011-07-27 | 山东建筑大学 | Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery |
| CN102292853A (en) * | 2009-02-04 | 2011-12-21 | 独立行政法人产业技术综合研究所 | Fiber electrodes for lithium secondary batteries, manufacturing method therefor, and lithium secondary batteries provided with fiber electrodes |
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| CN102292853A (en) * | 2009-02-04 | 2011-12-21 | 独立行政法人产业技术综合研究所 | Fiber electrodes for lithium secondary batteries, manufacturing method therefor, and lithium secondary batteries provided with fiber electrodes |
| CN102136567A (en) * | 2011-02-14 | 2011-07-27 | 山东建筑大学 | Preparing method of tin-nickel-carbon composite cathode material of lithium ion battery |
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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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