CN103022450B - Three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and preparation method thereof - Google Patents
Three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode and a preparation method thereof. The preparation method of the three-dimensional netted tin-copper-nickel-carbon nanotube alloy negative electrode comprises the following steps: firstly, chemically plating carbon nanotubes with a nickel layer of a certain thickness; secondly, uniformly dispersing nickle-plated CNTs (carbon nanotubes) into a tin-plating solution; thirdly, taking foamy copper as a current collector (a plating substrate), sequentially compositely plating a CU-(CNTs-Ni) composite plating layer with the thickness of 1-3 microns, and plating an Sn-(CNTs-Ni) composite plating layer with the thickness of 0.1-3 Mum; and finally, performing thermal treatment to obtain a three-dimensional composite network alloy electrode. The alloy negative electrode has the first discharge specific capacity of 620mAh/g, and after 200cycles, the specific capacity is attenuated by only 3-5%; the preparation method is simple in process; and the prepared alloy negative electrode is excellent in performance and is applicable to large-scale industrial 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 employing Cu-(CNTs-Ni) transition zone and connect active material and collector, and adopt the negative material and preparation method thereof of three-dimensional network kamash alloy of the carbon nano-tube of nickel plating modification.
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 efflorescence serious, 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 effects such as skin effect that conventional nano material has, small-size effect, toward contact, there is good electrical and thermal conductivity performance, 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 in 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 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.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.
Although the tin base alloy anode material function admirable that these methods are prepared, but be basis mainly with nanostructure, production cost is high, 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].
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 specification requirement is high, therefore, CNTs is carried out to surface modification and become CNTs application one of the method more widely that makes.As improved chemical plating nickel technologies of employing such as Chen little Hua, and by heat treatment, on CNTs surface, obtain continuous, smooth, uniform nickel coating, 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.Progress along with industrial expansion and scientific and technological progress, chemical nickel plating has become the very promising technology of a kind of tool, with other coating methods, compare, 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 of chemical plating solution is excellent, 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 is fine and close, and 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, 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 fundamentally 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 foam copper as collector (electroplated substrates), first electroplate certain thickness Cu-(CNTs-Ni) composite deposite, composite plating Sn-(CNTs-Ni again) composite deposite, last heat treatment obtains the three-dimensional composite network alloy electrode of tin copper nickel-CNTs.
Summary of the invention
The present invention is directed to the not good problem of alloy material of cathode cycle performance, proposition selects foam copper as collector, between active material layer (the tin copper nickel-carbon nano-tube composite bed obtaining after final step heat treatment) and collector, increase Cu-(CNTs-Ni) articulamentum, and CNTs in active material is carried out to chemical nickel plating processing, both improved the uniformity that in electroplating process, CNTs distributes in active material, can make again heat treatment afterproduct form multicomponent alloy, further improve the cycle performance of active material self.And in conjunction with the high strength of carbon nano-tube and the advantage of high conductivity, a kind of three-dimensional netted tin copper nickel-carbon nano-tube alloy anode that is connected active material and collector by Cu-(CNTs-Ni) and preparation method thereof has been proposed.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 three-dimensional netted tin copper nickel-carbon nano-tube alloy anode, comprises the following steps:
(1) first adopt chemical plating to CNTs plated nickel coating, then the CNTs after nickel plating is obtained to composite plating solution so that the concentration of 2 ~ 8g/L is dispersed to copper plating solution, so that the concentration of 1 ~ 5g/L is dispersed, to tin plating solution, obtain Composite Coatings solution of tin;
(2) adopt the composite plating solution obtaining in step (1), on foam copper, adopt direct current electrode position, plating Cu-(CNTs-Ni) composite deposite;
(3) plating of preparation in step (2) is had to foam copper heat treatment under protective atmosphere of Cu-(CNTs-Ni) composite deposite;
(4) adopt plating that step (3) obtains the foam copper of Cu-(CNTs-Ni) composite deposite be substrate, adopt the Composite Coatings solution of tin of step (1) preparation, with method plating Sn-(CNTs-Ni) composite deposite of direct current electrode position;
(5) to the plating obtaining in step (4), there is the foam copper of Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) composite deposite to heat-treat, finally obtain the three-dimensional netted tin copper nickel-carbon nano-tube alloy anode being connected by Cu-(CNTs-Ni) transition zone.
Described CNTs specification is: external diameter is 10 ~ 100nm, and length is 0.5 ~ 10 μ m.
The thickness of the chemical Ni-plating layer on CNTs is 10 ~ 500nm.
The thickness of Cu-(CNTs-Ni) composite deposite that step (2) is described is 1 ~ 3 μ m; The thickness of Sn-(CNTs-Ni) composite deposite that step (4) is described is 0.1 ~ 3 μ m.
The hole count of described foam copper strips is distributed as 110PPI ~ 150PPI.
The heat-treat condition that step (3) adopts is, 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 10 ~ 20 hours.
The heat-treat condition that step (4) adopts is, the protective atmosphere of employing is argon gas or nitrogen or both mists, and heat treatment temperature is 120 ~ 280 ℃, and heat treatment time is 2 ~ 10 hours.
Three-dimensional netted tin copper nickel-carbon nano-tube alloy anode 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 0.5 ~ 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;
By the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 0.5 ~ 3 hour simultaneously again, and then magnetic agitation is 8 ~ 24 hours, then CNTs is separated from pretreatment liquid, finally CNTs is dried to 10 ~ 24 hours;
(2) then adopt the nickel coating that chemical plating is 10 ~ 500nm to CNTs plated thickness.
Formula and the condition of chemical nickel plating are as follows:
(3) adopt in step (2), obtain cover nickel CNTs, on foam Copper Foil, adopting direct current electrode position plated thickness is Cu-(CNTs-Ni) composite deposite of 1 ~ 3 μ m.
Formula and the condition of electroplating Cu-(CNTs-Ni) 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;
CNTs-Ni 2~8g/L；
PH value 8.2 ~ 8.8;
30 ~ 50 ℃ of temperature;
Cathode-current density 0.5 ~ 1 A/dm
2;
(4) plating obtaining with step (3) Copper Foil heat treatment 10 ~ 20h at 200 ℃ ~ 300 ℃ of Cu-(CNTs-Ni) composite deposite, take it as substrate again, adopt direct current electrode position, plated thickness is Sn-(CNTs-Ni) composite deposite of 0.1 ~ 3 μ m.
Formula and the condition of electroplating Sn-(CNTs-Ni) are as follows:
Sodium stannate 75 ~ 90 g/L;
NaOH 8 ~ 12g/L;
Hydrogen peroxide 0 ~ 50g/L;
CNTs-Ni 1~5g/L；
70 ~ 90 ℃ of temperature;
Cathode-current density 1 ~ 1.5A/dm
2;
(5) plating obtaining in step (4) is had to the Copper Foil of Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) composite deposite 120 ~ 280 ℃ of heat treatments 2 ~ 10 hours, finally obtain the three-dimensional netted tin copper nickel-carbon nano-tube alloy anode being connected by Cu-(CNTs-Ni) transition zone.
The present invention selects foam copper as collector, can increase greatly the specific area of electrode, and play certain cushioning effect for active material drastic change of stress in charge and discharge process, and improve to a certain extent the efficiency that lithium ion embeds and deviates from, thus improve the high rate performance of electrode.
The present invention powers on and has plated one deck Cu-(CNTs-Ni) composite deposite as the articulamentum between active material and collector at collector foam copper strips.The effect that increases the compound transition zone of Cu-(CNTs-Ni) has two aspects: 1.Cu-(CNTs-Ni) composite deposite intensity high, and after heat treatment, CNTs can connect active material and collector, thereby improves the adhesion between active material and collector; 2.CNTs can connect active material and collector, for the transmission of the electronics in electronics charge and discharge process provides passage.
The present invention proposes, before electroplating CNTs composite deposite, CNTs is carried out to chemical nickel plating processing: on the one hand, chemical plating the CNTs of nickel dam in electroplating process, more easily deposit in the middle of copper coating and tin coating, and improve CNTs distributing homogeneity in coating in electroplating process; On the other hand, the nickel dam 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 collector that is covered with Cu-(CNTs-Ni) composite deposite when plated surface is after Overheating Treatment, copper atom in coating and the counterdiffusion of the meeting of the copper atom in collector phase, 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 plating Sn-(CNTs-Ni) coating, exposed CNTs outside coating just can be covered by tin layer originally.During heat treatment, the metallic atom in Sn-(CNTs-Ni) coating spreads downwards, and formation can have take tin copper nickel-CNTs alloy anode that CNTs is 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 ~ 3 μ m that the present invention controls Cu-(CNTs-Ni) thickness of multiple plating, and preferred thickness is 1.5 ~ 2.5 μ m.The Main Function that this composite deposite plays in whole three-dimensional netted tin copper nickel-CNTs alloy anode is to work to connect collector and active material 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.
In the present invention, in the tin layer of electroplating, 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 0.5 ~ 10 μ m.Select this external diameter to be because the conductive capability of CNTs is relevant with external diameter, when 30nm is following, 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.Due to Sn-(CNTs-Ni in the present invention) maximum ga(u)ge of 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 to protrude from coating outside to improve the object of material specific surface, therefore the preferred CNTs length of the present invention is 1 ~ 3 μ m, and preferably external diameter is 10 ~ 20nm.
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.Three-dimensional netted tin copper nickel-CNTs alloy anode initial charge quality capacity prepared by the present invention is 600 ~ 800mAh/g.Three-dimensional netted tin copper nickel-CNTs alloy anode that the present invention prepares also possesses good cycle performance and rate charge-discharge performance simultaneously, special capacity fade only 3% ~ 5% 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 3 factors: 1, CNTs runs through between collector and active material, because CNTs itself has good conductivity and mechanical performance, can between active material and collector, 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, 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; 3, tinbase multicomponent alloy can carry out reversible alloy and removal alloying with lithium metal, copper, nickel metal implement are for good ductility and heat-conductivity conducting performance, when tin atom is combined formation intermetallic compound with copper, 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.
Compare with other inventive method, the present invention possesses following outstanding advantages:
1, propose between active material and collector, to increase Cu-(CNTs-Ni) transition zone, both strengthened the mechanical connection between active material and collector, conductive channel is provided again; 2, 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, further improve the cycle performance of active material self; 3, production cost is lower, and preparation process is simple; 4, 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; 5, heat treatment temperature is lower, and the time is shorter, reduce production costs, and energy savings.
Cu-(CNTs – Ni involved in the present invention) surface topography of composite deposite and Sn-(CNTs-Ni) composite deposite, 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.
Accompanying drawing explanation
Fig. 1 is that the present invention electroplates Sn-(CNTs-Ni) composite deposite low range surface topography microgram afterwards;
Fig. 2 is that the present invention electroplates Sn-(CNTs-Ni) after composite deposite compared with high magnification surface topography microgram.
Embodiment:
Embodiment 1:
(1) CNTs is carried out to removal of impurities and dispersion treatment, selecting external diameter is 10 ~ 20nm, and length is 1 ~ 3 μ m carbon nano-tube,
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;
By the ultrasonic concussion of above-mentioned pretreatment liquid, mechanical agitation is 2 hours simultaneously again, and then magnetic agitation is 10 hours, then CNTs is separated from pretreatment liquid, finally CNTs is dried to 24 hours;
(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) adopt in step (2), obtain cover nickel CNTs, the foam copper that is 120PPI in specification is that in substrate, to adopt the method for direct current electrode position, plated thickness be the Cu-(CNTs-Ni of 2 μ m) composite deposite.
Plating Cu-(CNTs-Ni) formula and the condition of composite deposite are as follows:
Cupric pyrophosphate 60g/L;
Potassium pyrophosphate 320g/L;
Sodium potassium tartrate tetrahydrate 30mL/L;
Sodium dihydrogen phosphate 40g/L;
Ammoniacal liquor 2ml/L;
CNTs-Ni 8g/L；
PH value 8.2;
30 ℃ of temperature;
Cathode-current density 2A/dm
2;
(4) plating obtaining with step (3) Cu-(CNTs-Ni) foam copper of composite deposite; at 260 ℃, take nitrogen as protective atmosphere, heat treatment 20h, then take it as substrate; the method that adopts direct current electrode position, plated thickness is the Sn-(CNTs – Ni of 2 μ m) composite deposite.
Plating Sn-(CNTs – Ni) formula and the condition of composite deposite are as follows:
Sodium stannate 90g/L;
NaOH 12g/L;
Hydrogen peroxide 50g/L;
CNTs-Ni 5g/L；
Temperature 70 C;
Cathode-current density 1.5A/dm
2;
(5) plating obtaining in step (4) is had to Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) foam copper of composite deposite is at 200 ℃; take nitrogen as protective atmosphere; heat treatment 6 hours, obtains three-dimensional netted tin copper nickel-CNTs alloy anode.
Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 613mAh/g of this negative pole active principle, after 200 charging cycle, specific capacity still has 600mAh/g, its special capacity fade only 2%, and coulomb efficiency surpasses 98%.
Embodiment 2:
All the other steps are identical with embodiment 1, the foam copper that the specification of take is 120PPI is substrate, composite plating thickness is the Cu-(CNTs-Ni of 1 μ m) composite deposite, and then composite plating 2 μ m Sn-(CNTs-Ni) alloy layer, last 200 ℃ of heat treatments obtain three-dimensional netted tin copper nickel-CNTs alloy anode for 10 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 587mAh/g of this negative pole active principle, after 200 charging cycle, specific capacity still has 563.5mAh/g, its special capacity fade only 4%, and coulomb efficiency surpasses 96%.
Embodiment 3:
All the other steps are identical with embodiment 1.The foam copper that the specification of take is 120PPI is substrate, composite plating thickness is the Cu-(CNTs-Ni of 3 μ m) composite deposite, and then adopt the method for codeposition to electroplate 2 μ m Sn-(CNTs-Ni) coating, last 200 ℃ of heat treatments obtain three-dimensional netted tin copper nickel-CNTs alloy anode for 2 hours.Adopt conventional lithium ion battery method of testing, obtain the specific discharge capacity of the electric discharge first 607mAh/g of this negative pole active principle, after 100 charging cycle, specific capacity still has 588.8mAh/g, its special capacity fade only 3%, and coulomb efficiency surpasses 97%.
Claims (8)
1. a preparation method for three-dimensional netted tin copper nickel-carbon nano-tube alloy anode, is characterized in that, comprises the steps:
(1) first adopt chemical plating to carbon nano-tube plated nickel coating, then the carbon nano-tube after nickel plating is obtained to composite plating solution so that the concentration of 2～8g/L is dispersed to copper plating solution, so that the concentration of 1～5g/L is dispersed, to tin plating solution, obtain Composite Coatings solution of tin;
(2) adopt the composite plating solution obtaining in step (1), on foam copper, adopt direct current electrode position, plating Cu-(carbon nano-tube-Ni) composite deposite;
(3) plating of preparation in step (2) is had to foam copper heat treatment under protective atmosphere of Cu-(carbon nano-tube-Ni) composite deposite;
(4) adopt plating that step (3) obtains the foam copper of Cu-(carbon nano-tube-Ni) composite deposite be substrate, adopt the Composite Coatings solution of tin of step (1) preparation, adopt direct current electrode position, plating Sn-(carbon nano-tube-Ni) composite deposite;
(5) to the plating obtaining in step (4), there is the foam copper of Cu-(carbon nano-tube-Ni) composite deposite and Sn-(carbon nano-tube-Ni) composite deposite to heat-treat, finally obtain the three-dimensional netted tin copper nickel-carbon nano-tube alloy anode being connected by Cu-(carbon nano-tube-Ni) transition zone.
2. preparation method according to claim 1, is characterized in that: the carbon nano-tube specification of employing is: external diameter is 10～100nm, and length is 0.5～10 μ m.
3. according to the preparation method described in claim 1, it is characterized in that, the thickness of described nickel coating is 10～500nm.
4. according to the preparation method described in claim 1, it is characterized in that, the thickness of Cu-(carbon nano-tube-Ni) composite deposite that step (2) is described is 1～3 μ m; The thickness of Sn-(carbon nano-tube-Ni) composite deposite that step (4) is described is 0.1～3 μ m.
5. preparation method according to claim 1, is characterized in that, the hole count of described foam copper strips is distributed as 110PPI～150PPI.
6. preparation method according to claim 1, is characterized in that, the protective atmosphere that step (3) adopts is argon gas or nitrogen or both mists, and heat treatment temperature is 200～300 ℃, and heat treatment time is 10～20 hours.
7. preparation method according to claim 1, is characterized in that, the protective atmosphere that step (5) adopts is argon gas or nitrogen or both mists, and heat treatment temperature is 120～280 ℃, and heat treatment time is 2～10 hours.
8. three-dimensional netted tin copper nickel-carbon nano-tube alloy anode, is characterized in that, is the three-dimensional netted tin copper nickel-carbon nano-tube alloy anode being prepared from by the method described in claim 1～7 any one.
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