CN103022450A - 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 make the 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 the negative material of the three-dimensional network kamash alloy of the carbon nano-tube of employing nickel plating modification 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 efflorescence serious, 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-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.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.
Although the tin base alloy anode material function admirable that these methods are prepared, but mainly with nanostructure be the basis, production cost is high, and said method is difficult to solve, and 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].
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.In order fundamentally 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 foam copper as collector (electroplated substrates), electroplate first certain thickness Cu-(CNTs-Ni) composite deposite, composite plating Sn-(CNTs-Ni again) composite deposite, last heat treatment obtain 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, the selection foam copper is as collector, between active material layer (the tin copper nickel that obtains after the final step heat treatment-carbon nano-tube composite bed) and collector, increase Cu-(CNTs-Ni) articulamentum, and CNTs in the active material is carried out chemical nickel plating process, both improved the uniformity that CNTs distributes in the electroplating process in active material, can make again the 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 by Cu-(CNTs-Ni) connection active material and collector-carbon nano-tube alloy anode 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.
The preparation method of a kind of three-dimensional netted tin copper nickel-carbon nano-tube alloy anode may further comprise the steps:
(1) adopts first chemical plating to CNTs plated nickel coating, then the CNTs after the nickel plating is obtained composite plating solution with the concentration Uniform Dispersion of 2 ~ 8g/L to copper plating solution, to tin plating solution, obtain the Composite Coatings solution of tin with the concentration Uniform Dispersion of 1 ~ 5g/L;
(2) adopt the composite plating solution that obtains in the step (1), adopt direct current electrode position at foam copper, plating Cu-(CNTs-Ni) composite deposite;
(3) plating of preparation in the step (2) there is 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) there is the foam copper of Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) composite deposite to heat-treat to the plating that obtains in the step (4), finally obtains the three-dimensional netted tin copper nickel that connected by Cu-(CNTs-Ni) transition zone-carbon nano-tube alloy anode.
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 the CNTs is 10 ~ 500nm.
The thickness of the described Cu-of step (2) (CNTs-Ni) composite deposite is 1 ~ 3 μ m; The thickness of the described Sn-of step (4) (CNTs-Ni) composite deposite 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.
A kind of 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 removal of impurities and dispersion treatment, the present invention selects the CNTs specification to be: external diameter is 10 ~ 100nm, and length is 0.5 ~ 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.
Prescription and the condition of chemical nickel plating are as follows:
(3) adopt obtain in the step (2) cover nickel CNTs, adopting the direct current electrode position plated thickness at the foam Copper Foil is Cu-(CNTs-Ni) composite deposite of 1 ~ 3 μ m.
Prescription 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 that obtains with step (3) Copper Foil of Cu-(CNTs-Ni) composite deposite at 200 ℃ ~ 300 ℃ lower heat treatment 10 ~ 20h, again take it as substrate, adopt direct current electrode position, plated thickness is Sn-(CNTs-Ni) composite deposite of 0.1 ~ 3 μ m.
Prescription 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) Copper Foil that the plating that obtains in the step (4) is had Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) composite deposite is 120 ~ 280 ℃ of heat treatments 2 ~ 10 hours, finally obtains the three-dimensional netted tin copper nickel that connected by Cu-(CNTs-Ni) transition zone-carbon nano-tube alloy anode.
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 lithium ion and embed and the efficient of deviating from, thereby improve the high rate performance of electrode.
The present invention powers at collector foam copper strips and has plated one deck Cu-(CNTs-Ni) composite deposite as the articulamentum between active material and the collector.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 the collector; 2.CNTs can connect active material and collector, for the transmission of the electronics in the electronics charge and discharge process provides passage.
The present invention proposes before electroplating the CNTs composite deposite CNTs to be carried out chemical nickel plating and processes: on the one hand, chemical plating CNTs easier depositing in the middle of copper coating and the tin coating in electroplating process of nickel dam, 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 the CNTs and electrodeposited coating in the electroplating process, makes between CNTs and the electrodeposited coating in conjunction with tightr.
When plated surface is covered with the collector of Cu-(CNTs-Ni) composite deposite after Overheating Treatment, copper atom in the coating is understood mutually counterdiffusion with the copper atom in the collector, 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 plating Sn-(CNTs-Ni) coating, the CNTs that originally exposes outside coating just can be covered by the tin layer.During heat treatment, the metallic atom in Sn-(CNTs-Ni) coating spreads downwards, and formation can have tin copper nickel take CNTs as network configuration-CNTs alloy anode.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 ~ 3 μ m with 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, 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.
Among the present invention, CNTs can be evenly distributed on the active material portion of whole negative pole in the tin layer of electroplating, 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 0.5 ~ 10 μ m.Select this external diameter to be because the conductive capability of CNTs is relevant with external 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 Sn-(CNTs-Ni among 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 more CNTs is reached protrude from the coating outside to improve the purpose of material specific surface, therefore the preferred CNTs length of the present invention is 1 ~ 3 μ m, and preferred external diameter is 10 ~ 20nm.
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 present invention preparation three-dimensional netted tin copper nickel-CNTs alloy anode initial charge quality capacity is 600 ~ 800mAh/g.The three-dimensional netted tin copper nickel that the present invention prepares-CNTs alloy anode also possesses good cycle performance and rate charge-discharge performance simultaneously, special capacity fade only 3% ~ 5% 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 3 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 collector, 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, 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; 3, the tinbase multicomponent alloy can carry out reversible alloy and removal alloying with lithium metal, copper, standby good ductility and the heat-conductivity conducting performance of nickel metal implement, when tin atom is combined the formation intermetallic compound with copper, 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, proposes between active material and collector, to increase Cu-(CNTs-Ni) transition zone, both strengthened the mechanical connection between active material and the collector, conductive channel is provided again; 2, 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, 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, reduces production costs energy savings.
Cu-(CNTs – Ni involved in the present invention) surface topography of composite deposite and Sn-(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 low range surface topography microgram afterwards;
Fig. 2 is that the present invention electroplates Sn-(CNTs-Ni) after the composite deposite than high magnification surface topography microgram.
Embodiment:
Embodiment 1:
(1) CNTs is carried out removal of impurities and dispersion treatment, selecting external diameter is 10 ~ 20nm, and length is 1 ~ 3 μ m carbon nano-tube,
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 10 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) adopt obtain in the step (2) cover nickel CNTs, be that the foam copper of 120PPI is the method that direct current electrode position is adopted in substrate in specification, plated thickness is the Cu-(CNTs-Ni of 2 μ m) composite deposite.
Plating Cu-(CNTs-Ni) prescription 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 that obtains with step (3) Cu-(CNTs-Ni) foam copper of composite deposite; take nitrogen as protective atmosphere, heat treatment 20h is again take it as substrate under 260 ℃; adopt the method for direct current electrode position, plated thickness is the Sn-(CNTs – Ni of 2 μ m) composite deposite.
Plating Sn-(CNTs – Ni) prescription 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 that obtains in the step (4) is had Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) foam copper of composite deposite is under 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 first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 98%.
Embodiment 2:
All the other steps are identical with embodiment 1, foam copper take specification as 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 obtained three-dimensional netted tin copper nickel-CNTs alloy anode in 10 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 96%.
Embodiment 3:
All the other steps are identical with embodiment 1.Foam copper take specification as 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 obtained three-dimensional netted tin copper nickel-CNTs alloy anode in 2 hours.Adopt conventional lithium ion battery method of testing, obtain the first discharge specific discharge capacity 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 enclosed pasture efficient surpasses 97%.
Claims (8)
1. the preparation method of three-dimensional netted tin copper nickel-carbon nano-tube alloy anode is characterized in that, comprises the steps:
(1) adopts first chemical plating to CNTs plated nickel coating, then the CNTs after the nickel plating is obtained composite plating solution with the concentration Uniform Dispersion of 2 ~ 8g/L to copper plating solution, to tin plating solution, obtain the Composite Coatings solution of tin with the concentration Uniform Dispersion of 1 ~ 5g/L;
(2) adopt the composite plating solution that obtains in the step (1), adopt direct current electrode position at foam copper, plating Cu-(CNTs-Ni) composite deposite;
(3) plating of preparation in the step (2) there is 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, adopt direct current electrode position, plating Sn-(CNTs-Ni) composite deposite;
(5) there is the foam copper of Cu-(CNTs-Ni) composite deposite and Sn-(CNTs-Ni) composite deposite to heat-treat to the plating that obtains in the step (4), finally obtains the three-dimensional netted tin copper nickel that connected by Cu-(CNTs-Ni) transition zone-carbon nano-tube alloy anode.
2. preparation method according to claim 1, it is characterized in that: the CNTs specification of employing is: external diameter is 10 ~ 100nm, length is 0.5 ~ 10 μ m.
3. the preparation method described in according to claim 1 is characterized in that the thickness of described nickel coating is 10 ~ 500nm.
4. the preparation method described in according to claim 1 is characterized in that the thickness of the described Cu-of step (2) (CNTs-Ni) composite deposite is 1 ~ 3 μ m; The thickness of the described Sn-of step (4) (CNTs-Ni) composite deposite 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 that is prepared from by the described method of claim 1 ~ 7 any one-carbon nano-tube alloy anode.
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| CN106591926A (en) * | 2016-12-09 | 2017-04-26 | 济南大学 | Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel |
| CN108539153A (en) * | 2018-03-27 | 2018-09-14 | 电子科技大学 | Lithium metal composite negative pole material and preparation method thereof |
| CN108585125A (en) * | 2018-04-04 | 2018-09-28 | 南京大学 | The carbon-based cupro-nickel combination electrode of nitrate nitrogen, preparation method and applications in reductive water |
| CN110938844A (en) * | 2019-11-13 | 2020-03-31 | 华南理工大学 | Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof |
| CN114583118A (en) * | 2020-11-30 | 2022-06-03 | 松山湖材料实验室 | Carbon-coated tin nanowire array cathode material and preparation method and application thereof |
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| US20110195311A1 (en) * | 2010-02-08 | 2011-08-11 | Beom-Kwon Kim | Negative electrode for rechargeable lithium battery, method for manufacturing thereof, and rechargeable lithium battery comprising the same |
| 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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| CN101207199A (en) * | 2007-12-14 | 2008-06-25 | 华南师范大学 | Lithium ion battery tin-carbon nanometer tube negative pole material and preparation method thereof |
| US20110195311A1 (en) * | 2010-02-08 | 2011-08-11 | Beom-Kwon Kim | Negative electrode for rechargeable lithium battery, method for manufacturing thereof, and rechargeable lithium battery comprising the same |
| 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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| CN106591926A (en) * | 2016-12-09 | 2017-04-26 | 济南大学 | Method for preparing CNTs-porous nickel/nickel oxide hydrogen evolution reaction catalyst on surface of steel |
| CN106591926B (en) * | 2016-12-09 | 2018-10-02 | 济南大学 | In the method that steel surface prepares the porous nickel nickel evolving hydrogen reaction catalyst of CNTs- |
| CN108539153A (en) * | 2018-03-27 | 2018-09-14 | 电子科技大学 | Lithium metal composite negative pole material and preparation method thereof |
| CN108585125A (en) * | 2018-04-04 | 2018-09-28 | 南京大学 | The carbon-based cupro-nickel combination electrode of nitrate nitrogen, preparation method and applications in reductive water |
| CN108585125B (en) * | 2018-04-04 | 2020-12-04 | 南京大学 | Carbon-based copper-nickel composite electrode for reducing nitrate nitrogen in water, preparation method and application thereof |
| CN110938844A (en) * | 2019-11-13 | 2020-03-31 | 华南理工大学 | Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof |
| CN110938844B (en) * | 2019-11-13 | 2021-09-21 | 华南理工大学 | Self-supporting three-dimensional copper-tin alloy material and preparation method and application thereof |
| CN114583118A (en) * | 2020-11-30 | 2022-06-03 | 松山湖材料实验室 | Carbon-coated tin nanowire array cathode material and preparation method and application thereof |
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