CN103022424B - 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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- CN103022424B CN103022424B CN201210562192.6A CN201210562192A CN103022424B CN 103022424 B CN103022424 B CN 103022424B CN 201210562192 A CN201210562192 A CN 201210562192A CN 103022424 B CN103022424 B CN 103022424B
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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 manufacture field, relate to a kind of lithium ion battery cathode material and its preparation method, particularly relate to a kind of tin base alloy anode material that the carbon nano-tube of nickel plating modification adulterates and preparation method thereof that adopts.
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 electric tool and notebook computer of the contour electric weight demand of current electric automobile, 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 the alloy material such as tin (Sn:994mAh/g) sill and silicon materials that, has a high-energy-density becomes the emphasis of 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 deintercalation 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, main method is to prepare 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 adulterate or carry out compound with other materials, as mix third phase metal, silicon materials, the material with carbon elements such as carbon nano-tube (CNTs).
Carbon nanomaterial superior performance, except having the nano effect such as skin effect, small-size effect that conventional nano material has, there is good electrical and thermal conductivity performance toward contact, the characteristic that high intensity etc. are unique, thereby be very 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, lightweight, and hexagonal structure connects perfect, has many abnormal mechanics, electricity and chemical property.Graphene is not only one the thinnest in known materials, also very firmly hard; As simple substance, it is all faster than known conductor that it at room temperature transmits the speed of electronics.In recent years along with its wide application prospect of going deep into of carbon nano-tube and nano materials research also constantly shows.
Carbon nano-tube and Graphene all have good mechanical property and good conductivity, carry 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-basednano-architectured electrode assembly for rechargeable lithium batteries.Journal ofPower Sources.188 (2009) 578 – 582] taking 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/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 taking carbon nano-tube (CNTs) as template, prepared the tin base cathode material being wrapped up by CNTs by chemical vapour deposition technique, 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 effective multi-wall carbon nano-tube polyelectrolyte; 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.Chinese patent CN101207199A by carbon nanotube dispersed to having added in the middle of the sulfuric acid of additive and the composite plating bath of stannous sulfate, re-plating has obtained tin-carbon nanometer tube combination electrode, for pure tin electrode, its cycle performance has also obtained larger lifting.
The work that CNTs is applied to alloy anode field has obtained certain effect, but with regard to CNTs, its surface curvature is large, difficulties in dispersion, and technical requirement is high, therefore, CNTs is carried out to surface modification and become CNTs application one of the method more widely that makes.As Chen little Hua etc. adopts improved chemical plating nickel technology, and by heat treatment, obtain continuous, smooth, uniform nickel coating on CNTs surface, greatly reduced the application threshold of CNTs.
Chemical plating is redox reaction effect to occur at no current in same solution during by (without exterior power) by reducing agent, thereby makes metal ion reduce deposition at the lip-deep a kind of nickel plating process of self-catalysis.Along with the progress of 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 tool has the following advantages: 1. metal lining on the part that can make at various materials such as trip metal, semiconductor and non-conductors; 2. no matter how complicated the geometry of part is, all places that can touch solution can obtain the coating of even thickness, the dispersibility excellence of chemical plating solution, be not subject to the prophet of External Shape complexity, without significantly edge effect, be therefore particularly suitable for the plating of complex parts, pipe fitting inner wall, blind bored member; 3. process equipment is simple, without power supply, transmission system and auxiliary electrode, simple to operate; 4. coating densification, hole is few; 5. adhesion is due to electrodeposited coating; 6. coating often has special chemistry, mechanics or magnetic property.
Chemical nickel plating, as one of field of surface treatment new technology with fastest developing speed, with its excellent functional coating, is all widely used at nearly all industrial department.CNTs is carried out to surface modification work and has had certain basis, but by modification the CNTs work that is applied to again tin base alloy anode have not been reported.
Although the research about tin base alloy anode has had part element task, still has certain distance apart from the industrialization of tin base alloy anode material.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.
Summary of the invention
The object of the invention is the problem not good for alloy material of cathode cycle performance, propose tin nickel alloy negative of a kind of carbon nano-tube enhancing and preparation method thereof.The tin nickel alloy negative that this carbon nano-tube strengthens has carried out chemical nickel plating processing to CNTs while preparation, both improved the uniformity that in electroplating process, CNTs distributes in active material (the tin nickel-carbon nano-tube composite bed obtaining after final step heat treatment), can make again 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.
A preparation method for the tin nickel alloy negative that carbon nano-tube strengthens, comprises the steps:
(1) first adopt chemical plating to CNTs plated nickel coating, then that the CNTs after nickel plating is dispersed to tin plating solution with the concentration of 2 ~ 8g/L;
(2) taking 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 obtaining in step (2), finally obtain 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 CNTs is 10 ~ 500nm.
The thickness of Sn-(CNTs-Ni) composite deposite described in step (2) is 0.1 ~ 3 μ m.
When heat treatment, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 150 ~ 300 DEG C, and heat treatment time is 3 ~ 12 hours.
The tin nickel alloy negative that 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 to removal of impurities and dispersion treatment, the present invention selects CNTs specification to be: external diameter is 10 ~ 100nm, and length is 1 ~ 10 μ m, and preferably external diameter is 10 ~ 20nm, and preferred length is 1 ~ 3 μ m;
To CNTs treatment step be: the HCl solution that is first 18.25% by mass concentration adds in the container that contains CNTs, obtain the pretreatment liquid that CNTs content is 0.5 ~ 4g/L;
Again by ultrasonic above-mentioned pretreatment liquid concussion, mechanical agitation 0.5 ~ 3 hour simultaneously, then magnetic agitation 8 ~ 24 hours, then CNTs is separated from pretreatment liquid, finally by dry 10 ~ 24 hours of CNTs;
(2) then adopt the nickel coating that chemical plating is 10 ~ 500nm to CNTs plated thickness, then by dispersed the CNTs after nickel plating to tin plating solution, wherein the content of CNTs-Ni is 2 ~ 8g/L.
Formula and the condition of chemical nickel plating are as follows:
(3) taking 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.
Formula 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 DEG C of temperature;
Cathode-current density 1 ~ 1.5A/dm
2;
(4) to the Copper Foil of plating Sn-(CNTs-Ni) composite deposite obtaining in step (3) 150 ~ 300 DEG C of heat treatments 3 ~ 12 hours, finally obtain CNTs strengthen tin nickel alloy negative.
The present invention proposes, before plating CNTs composite deposite, CNTs is carried out to chemical plating processing: on the one hand, more easily deposit in the middle of tin coating in electroplating process with the CNTs of chemical deposit, and improve CNTs distributing homogeneity in coating in electroplating process; On the other hand, the coating on CNTs surface can strengthen the adhesion between CNTs and electrodeposited coating in electroplating process, makes between CNTs and electrodeposited coating in conjunction with tightr.
The present invention selects metallic nickel as object in the time of chemical plating, because nickel is high conductive metal material, and there is part report that nickel is applied in the middle of alloy anode, form multicomponent alloy with tin, the stress of lithium ion in the time embedding in buffering charge and discharge process, thereby the cycle performance of raising alloy anode.
In the present invention, in the time of heat treatment, the metallic atom in Sn-(CNTs-Ni) coating spreads downwards, and formation can have the CNTs-tin nickel alloy negative taking CNTs as network configuration.CNTs serves as skeleton in alloy anode, cushions greatly the stress that in charge and discharge process, volumetric expansion is shunk, thereby greatly improves the cycle performance of alloy anode.
In the present invention, in coating, CNTs can be evenly distributed on the active material portion of whole negative pole, part CNTs is through the intergranule of active material, thus the binding ability between enhanced activity material grains, thus the possibility that active material comes off from matrix is reduced.Due to the good conductive capability of CNTs, the speed that electronics moves in active material is strengthened greatly, alloy anode rate charge-discharge performance prepared by the present invention is outstanding simultaneously.In addition, in charge and discharge process, part active material still can produce be full of cracks, but due to connection and the conductive channel effect of CNTs, make this part material can bring into play preferably its charge-discharge performance, 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, below 30nm time, external diameter is less, and electric conductivity is better, and in conjunction with CNTs cost, it is 10 ~ 20nm that the present invention preferentially selects CNTs external diameter.Because the maximum ga(u)ge of Sn-in the present invention (CNTs-Ni) coating is about 3 μ m, CNTs length is long, can cause most of CNTs cross direction profiles in the middle of coating and cannot make more CNTs reach the object that protrudes from coating outside, therefore the preferred CNTs length of the present invention is 1 ~ 3 μ m.
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.
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.The tin nickel alloy negative initial charge quality capacity that CNTs prepared by the present invention 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 10C discharging condition, after its 200 times circulations, specific capacity still can reach 475mAh/g.This is the result being 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 the high rate charge-discharge performance of material is significantly improved; 2, tinbase multicomponent alloy can carry out reversible alloy and removal alloying with lithium metal, nickel metal implement is for good ductility and heat-conductivity conducting performance, when tin atom is combined formation intermetallic compound with nickle 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.
Compared with other inventive method, the present invention possesses following outstanding advantages:
1, CNTs is carried out to chemical nickel plating processing, improve the uniformity that in electroplating process, CNTs distributes in active material, can make again 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, reduce production costs, and energy savings.
Related Coating composition in the present invention, by measuring with Rigaku D/MAX-RB X-ray diffraction instrument.
The surface topography of Sn-(CNTs-Ni) composite deposite involved in the present invention, measures 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.
Brief description of the 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 Sn-(CNTs-Ni) composite deposite heat treatment surface topography microgram afterwards again.
Embodiment:
Be intended to further illustrate the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1:
(1) CNTs is carried out to removal of impurities and dispersion treatment, select CNTs specification to be: external diameter is 10 ~ 20nm, length is 1 ~ 3 μ m;
To CNTs treatment step be: the HCl solution that is first 18.25% by mass concentration adds in the container that contains CNTs, obtain the pretreatment liquid that CNTs content is 2g/L;
Again by ultrasonic above-mentioned pretreatment liquid concussion, mechanical agitation 2 hours simultaneously, then magnetic agitation 8 hours, then CNTs is separated from pretreatment liquid, finally by dry 24 hours of CNTs;
(2) then adopt the nickel coating that chemical plating is 100nm to CNTs plated thickness,
Formula and the condition of chemical nickel plating are as follows:
(3) taking Copper Foil as substrate, adopt the composite plating bath of following formula, adopting direct current electrode position to prepare thickness is 2 μ m Sn-(CNTs-Ni) composite deposites.
Formula 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 DEG C of temperature;
Cathode-current density 1.5A/dm
2;
(4) to the Copper Foil of plating Sn-(CNTs-Ni) composite deposite obtaining in step (3) at 200 DEG C taking nitrogen as protective atmosphere, heat treatment 6 hours, finally obtain CNTs strengthen tin nickel alloy negative.
Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 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 coulomb efficiency exceedes 98%.
Embodiment 2:
All the other steps are identical with embodiment 1.Last 200 DEG C of heat treatments obtain the tin nickel alloy negative that CNTs strengthens for 12 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 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 coulomb efficiency exceedes 98%.
Embodiment 3:
All the other steps are identical with embodiment 1.Last 200 DEG C of heat treatments obtain the tin nickel alloy negative that CNTs strengthens for 3 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 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 coulomb efficiency exceedes 98%.
Claims (6)
1. a preparation method for the tin nickel alloy negative that carbon nano-tube strengthens, is characterized in that, comprises the steps:
(1) first adopt chemical plating to carbon nano-tube plated nickel coating, then that the carbon nano-tube after nickel plating is dispersed to tin plating solution with the concentration of 2～8g/L;
(2), taking Copper Foil as substrate, in the tin plating solution that is dispersed with nickel-plating carbon nanotube that employing step (1) obtains, adopt direct current electrode position, preparation Sn-(carbon nano-tube-Ni) composite deposite;
(3) there is the Copper Foil of Sn-(carbon nano-tube-Ni) composite deposite to heat-treat to the plating obtaining in step (2), finally obtain the tin nickel alloy negative that carbon nano-tube strengthens.
2. the preparation method of the tin nickel alloy negative that carbon nano-tube according to claim 1 strengthens, is characterized in that: described carbon nano-tube specification is: external diameter is 10～100nm, length is 1～10 μ m.
3. the preparation method of the tin nickel alloy negative that carbon nano-tube according to claim 1 strengthens, is characterized in that, the thickness of the chemical Ni-plating layer in carbon nano-tube is 10～500nm.
4. the preparation method of the tin nickel alloy negative that carbon nano-tube according to claim 1 strengthens, is characterized in that: the thickness of Sn-(carbon nano-tube-Ni) composite deposite described in step (2) is 0.1～3 μ m.
5. the preparation method of the tin nickel alloy negative that carbon nano-tube according to claim 1 strengthens; it is characterized in that: when heat treatment; the protective atmosphere adopting is argon gas or nitrogen or both mists, and heat treatment temperature is 150～300 DEG C, 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 the carbon nano-tube that is prepared from by the method described in claim 1～5 any one strengthens.
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