CN103490053A - CNTS-doped tin oxide negative electrode material for lithium-ion battery and preparation method thereof - Google Patents
CNTS-doped tin oxide negative electrode material for lithium-ion battery and preparation method thereof Download PDFInfo
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention discloses a CNTs (carbon nanotubes)-doped tin oxide negative electrode material for a lithium-ion battery and a preparation method thereof. The preparation method comprises the following steps: firstly, compositely electroplating a CNTs-doped tin plating layer with the thickness of 10-15 microns on one side of the surface of a substrate of a pretreated copper strip; and secondly, anodizing the material obtained in the first step to obtain a mesoporous oxide, and performing heat treatment to finally obtain the lithium-ion battery negative electrode material with CNTs-uniformly-doped mesoporous tin oxide layer on one side of the surface of the substrate of the copper strip. The mesoporous diameter is 3-10nm and the obtained oxide layer has the thickness of 5-10 microns. The first specific discharge capacity of the lithium-ion battery negative electrode material can be as high as 650mAh/ g, and after 50 cycles, the specific capacity is attenuated by only 0.8%-5%. The preparation method is simple in process, and large-scale industrial production can be carried out.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material, particularly a kind of CNTs doped stannum oxide negative material and preparation method thereof.
Background technology
Lithium ion battery has that high-energy-density, high power density, security performance are good, the advantage such as have extended cycle life, and does not contain the polluters such as lead, cadmium, mercury, is a kind of comparatively desirable energy storage device.Negative material, as one of core component of lithium ion battery, has material impact to improving capacity of lithium ion battery and cycle life, has obtained showing great attention to of academia and industrial circle.The negative material of suitability for industrialized production is carbon class material, and its theoretical specific capacity is 372mAh/g, and the carbon capacity of negative plates of practical application has at present approached its theoretical specific capacity very much, and the possibility that further improves this material specific capacity is little.With social progress and scientific and technical development, the contour energy equipment that needs of electric automobile is more and more higher to the requirement of lithium ion battery, and the capacity of existing lithium ion battery can not meet the demand of contemporary electronic industry.Therefore, the negative material of seeking a kind of high-energy-density becomes present material worker's main target.
Tin oxide is a kind of candidate that has very much prospect to substitute carbon negative electrode material of lithium ion cell; there is higher Theoretical Mass specific capacity (990mAh/g; almost three times of material with carbon element); various countries scientists' extensive concern [H.Uchiyama et al., Electrochem.Commun.10 (2008) 52-55 have been subject at present; M.Zubair et al., Scripta Mater.67 (2012) 665-668; C.Wang et al., J.Phys.Chem.C116 (2012) 4000-4011].These research work mainly adopt hydro thermal method or chemical deposition, and then heat treatment obtains lithium ion battery negative material, the initial charge specific capacity is higher, but tin oxide volume change in lithium ion embeds and deviates from process is very large, easily cause the material efflorescence to destroy, cause charge-discharge performance not good.
Meso-hole structure to a certain extent can buffer oxide tin and lithium alloy efflorescence process in volumetric expansion, reach the purpose that improves the material cycle performance.The tin oxide structure be widely studied at present mainly contains nano-array, hollow nanospheres and meso-hole structure etc.In meso-hole structure, there is a large amount of holes in material, can embed with the change in volume of deviating from and bring huge cushion space at lithium ion for tin oxide, stress and distortion that when the buffering lithium ion embeds, lattice variations produces, thereby while making the type material as negative material, in charge and discharge process, after lithium ion repeatedly embeds, it still can keep its original form.Because meso-hole structure tin oxide negative material possesses the performance of excellence like this, obtain the extensive concern of academia.As Shiva etc. utilizes hydro thermal method to prepare the meso-porous titanium dioxide tin of hole at 2～7.5nm, the cathode of lithium battery cycle performance prepared with this material is far superior to simple Sn negative material, and the first charge-discharge coulombic efficiency reaches 95%[K.Shiva, M.S.R.N.Kiran, U.Ramamurty, S.Asokan, A.J.Bhattacharyya, J.Solid State Electrochem.16 (2012) 3643-3649].The use hydro thermal methods such as Uchiyama have prepared cancellated tin oxide nano monocrystalline in the aqueous solution, the cathode of lithium battery prepared with this material discharge capacity first reaches 900mAh/g[H.Uchiyama, E.Hosono, I.Honma, H.Zhou, H.Imai, Electrochem.Commun.10 (2008) 52-55].Although the tin oxide negative material that these work are prepared has higher specific capacity, its complicated process of preparation, cost is higher, and production efficiency is low, therefore still need further to improve technique, just can be applicable to industrial production.
Anodic oxidation refers in the middle of suitable electrolyte and to pass to anode current using metal or metal alloy as anode, makes anode surface obtain the method for oxide-film.Yang etc. be take ammonium fluoride solution as electrolyte carries out anodic oxidation, have made Nano tube array of titanium dioxide [D.Yang, H.Park, H.Kim, S.Cho, W.Y.Choi, J.Electroceram.23 (2009) 159-163].Anodic oxidation is because its principle is simple, and technological requirement is low, is applicable to suitability for industrialized production, thereby is used widely in field of surface treatment.
The people's such as Lin Kezhi research is found, for the oxide cathode material of tin, due to the different (Li of Gibbs free energy of compound
2o:562.1kJ/mol; SnO
2: 256.8kJ/mol), the actuating force difference of reaction, so form the voltage platform of 1.58V when cycle charging first, produced Li at negative pole
2o.Due to Li
2the formation of O is irreversible, and this has just caused the larger irreversible capacity of circulation first; Simultaneously, due to tin atom comparatively softness and the low cluster that easily is gathered into of fusing point, once form cluster, just there will be two-phase section in material, its volume does not mate and easily causes capacity attenuation in cyclic process [Lin Kezhi, Wang Xiaolin, Xu Yanhui, power technology, 29 (2005) 62-65].Based on above problem, researcher is by adulterating to realize the study on the modification to the tin oxide negative material.Morales etc. pass through at SnO
2the a small amount of Mo of middle doping improves electrochemistry cycle performance [J.Morales, L.Sanchez, J.Electrochem.Soc.146 (1999) 1640-1642].Wang etc. combine tin-oxide and graphite by microemulsion synthesis method, have alleviated the efflorescence [Y.Wang, J.Y.Lee, B.H.Chen, J.Electrochem.Soc.151 (2004) A563-A570] of tin base cathode electrode in the electrochemistry cyclic process.Because CNTs (carbon nano-tube) has excellent mechanical property, (tensile strength reaches 50～200GPa, is 100 times of steel; Modulus of elasticity can reach 1TPa, suitable with adamantine modulus of elasticity, is about 5 times of steel; Good pliability, after the hydraulic pressure through 1011MPa, still can restore to the original state rapidly), and excellent electric property (on carbon nano-tube, the P electronics of carbon atom forms large-scale delocalized pi-bond, conjugation is remarkable), be subject to extensive concern in the battery material field, especially CNTs doping vario-property tin base cathode material is a large study hotspot [H.Zhang et al., Electrochimica Acta59 (2012) 160-167].
Summary of the invention
The problem such as high for above-mentioned existing tin oxide negative material cost, that cycle performance is poor, environmental pollution is comparatively serious, the invention provides that a kind of microstructure homogeneous, electric conductivity and cycle performance are good, the CNTs doped stannum oxide negative material that can be used for lithium battery and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of doped stannum oxide of the CNTs for lithium battery negative material, with the CNTs(carbon nano-tube in copper strips substrate surface one side) negative material of doped tin oxide layer, described CNTs doped tin oxide layer is to be electroplate with CNTs doped tin coating in copper strips substrate surface one side, then adopt anode oxidation process to form CNTs doped stannum oxide film, through Overheating Treatment, form again, this CNTs doped stannum oxide negative material has meso-hole structure, the CNTs proportion is 3.5%～4.5%, mesoporous diameter is 3～10nm.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material comprises the following steps:
(1) at the pretreated copper strips substrate surface one side composite plating CNTs doped tin coating of process, described thickness of coating is 10～15 μ m, preferably 11～13 μ m;
(2) step (1) is electroplated to resulting materials and carry out anodic oxidation, the time is 0.5～2 hour, preferably 1～1.5 hour;
(3) step (2) resulting materials is heat-treated, protective atmosphere is argon gas, and temperature is 150～400 ℃, preferably 200～380 ℃; Time is 0.5～2 hour, preferably 1～1.5 hour.
Above three steps all have irreplaceable effect to the impact of material property in the present invention, lack a step, will have a huge impact material property.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, the pretreatment condition of the described copper strips substrate of step (1) is specific as follows:
1) oil removing
Preparation adopts while removing oil solution remove oil formula and remove oil temperature is:
Solution used herein, solvent is deionized water;
2) activation
The activating recipe and the activation temperature that during the preparation activated solution, adopt are:
Sulfuric acid 25～75g/L;
The temperature room temperature;
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, the composite plating condition of the tin metal layer of the described even carbon nanotube doping of step (1) is as follows:
The formula and the condition that when 1) CNTs doped tin solution is plated in preparation, adopt are:
The copper strips substrate is placed on continuous electric plating device, controls current density and electroplating temperature, electroplate and obtain CNTs doped tin coating.
The oxidation recipes and the condition that while 2) preparing anodic oxidation solution, adopt are:
The boric acid of amount of calculation is dissolved in the deionized water of institute's dose volume 1/3, then deionized water is added, constantly stir and make its dissolving, after again sodium sulphate being dissolved, add in solution, solution is heated to 25～50 ℃, and carries out magnetic agitation, obtain anodic oxidation solution;
The resulting material of step (1) is placed in to the oxidation trough that anodic oxidation solution is housed, controls current density, oxidizing temperature and oxidization time, obtain the CNTs doped tin oxide layer.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, after the described anodic oxidation of step (2), in oxide skin(coating), carbon nano-tube proportion is 3.5%～4.5%.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, the described anodic oxidation condition of step (2) is as follows:
The oxidation recipes and the condition that during the preparation anodic oxidation solution, adopt are:
The boric acid of amount of calculation is dissolved in the deionized water of institute's dose volume 1/3, then deionized water is added, constantly stir and make its dissolving, after again sodium sulphate being dissolved, add in solution, solution is heated to 25～50 ℃, and carries out magnetic agitation, obtain anodic oxidation solution; The resulting material of step (1) is placed in to the oxidation trough that anodic oxidation solution is housed, controls current density, oxidizing temperature and oxidization time, obtain the CNTs doped tin oxide layer.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, the described heat treatment temperature of step (3) is controlled at 200～380 ℃, and the time is 0.5～2 hour, and protective gas is argon gas.
The above-mentioned CNT for lithium ion battery
sthe preparation method of doped stannum oxide negative material, after the described heat treatment of step (3), stannic oxide layer thickness is 10～15 μ m, mesoporous diameter is 3～10nm.
The present invention is for the CNT of lithium ion battery
sthe preparation method of doped stannum oxide negative material, select acid tin plating method in zinc-plated step (1).Acid zinc-plated current efficiency is high, current density is large, production efficiency is high, without heating, bath stability, large to the impurity tolerance, production cost is low, is applicable to large-scale industrialization production.Composite plating adopts at ultrasonic environment, make carbon nano-tube can uniform deposition in the middle of tin coating.
The present invention is for the CNT of lithium ion battery
sthe preparation method of doped stannum oxide negative material, realized evenly mixing carbon nano-tube in tin oxide, and carbon nano-tube proportion reaches 3.5%～4.5%.Carbon nano-tube has higher specific area and strong conductivity, therefore nanotube mixes effective conductivity of improving stannic oxide materials, carbon nano-tube, as support, is improved the stress state of thin-film material, thereby is improved the cycle performance of tin oxide negative material simultaneously.
The present invention adopts anode oxidation method, and oxidizing temperature is at 20～50 ℃, and temperature is higher, the speed of anodic oxidation corrosion is faster, can enhance productivity, but excess Temperature easily causes the oxidation film hyperoxidation, produce defect, therefore preferably 38～42 ℃ of anodizing temperatures of the present invention.
CNT for lithium ion battery of the present invention
sthe doped stannum oxide negative material, its implementation is first by plating CNTs doped tin, then anodic oxidation, last Low Temperature Heat Treatment.Heat treatment temperature is larger on the material property impact, and heat treatment temperature is too low, atom locomotivity deficiency, and crystallization rate is slow, affects production efficiency, or generates other non-target substance phases, and then affects the performance of material.Heat treatment temperature is too high; can cause crystallization excessive; the most directly impact is for may change compound structure; obtain other non-target substance phase structure; and to the requirement of equipment for Heating Processing also corresponding increasing; composition requirement to protective gas also can be stricter, and unnecessary high temperature can cause cost to increase simultaneously.Therefore, it is 150～400 ℃ that the present invention selects heat treatment temperature, is preferably 200～380 ℃.Heat treatment time is also a very important factor.Sufficient heat treatment time is the basis that obtains the stable homogeneous phase structure, and heat treatment time is too short, and crystallization is incomplete, does not form the phase of desired structure, does not reach the requirement of design of material; Heat treatment time is long, and material has formed the phase of desired structure in heat treatment process, and remaining heat treatment time is the waste of the energy, has increased industrial cost.The invention provides suitable heat treatment time is 0.5～6 hour, is preferably 1～2 hour.
It is high that lithium ion battery negative material of the present invention has a charging and discharging capacity, the advantages such as cycle performance excellence.Initial charge quality capacity is 560～600mAh/g, also possesses the good characteristic of cycle performance simultaneously, special capacity fade only 0.8%～5% after 50 circulations, this is the result produced by following 2 factors: 1, tin oxide has meso-hole structure, and mesoporous hole can play the volume cushioning effect for tin oxide in lithium ion embeds and deviates from process.Therefore, at lithium ion, embed in process, mesoporous material can make negative material bear larger cubic deformation, thereby makes the prepared negative material of the present invention still can in cyclic process, keep its original form; 2, the lithium ion battery negative material that the present invention prepares has evenly mixed carbon nano-tube, and its carbon nano-tube proportion reaches 3.5%～4.5%.Carbon nano-tube has high specific area, in lithium ion embeds and deviates from process, the change in volume of buffer oxide tin, homodisperse carbon nano-tube can be used as the support of stannic oxide materials simultaneously, improve the stress of thin-film material in lithium ion embeds and deviates from process, thereby improve the cycle performance of stannic oxide materials.
Compared with prior art, beneficial effect of the present invention is:
1, the doping of carbon nano-tube has promoted electric conductivity, makes the rear special capacity fade of circulation obviously reduce simultaneously, is only 0.8～5%; 2, can be used in industry very ripe plating, anodic oxidation device fabrication, and adopt the method for rapid thermal treatment to prepare lithium ion battery negative material, be conducive to the suitability for industrialized production of product; 3, use non-cyanide solution for electroplating solution, environmentally safe, meet environmental requirement; 4, acid zinc-plated with the obvious advantage than alkaline tin plating, to electroplate evenly, cost is controlled; 5, heat treatment temperature is lower, and the time is shorter, reduce production costs, and energy savings.
The accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure that obtains CNTs doped stannum oxide cell negative electrode material in the embodiment of the present invention; In Fig. 1, abscissa is sweep limits (2-Theta), and ordinate is diffracted intensity (Intensity);
Fig. 2 is the process chart that the present invention prepares lithium ion CNTs doped stannum oxide cell negative electrode material.
Embodiment
Following examples are intended to further illustrate the present invention, and unrestricted the present invention.
Related material composition in the present invention, by measuring with Rigaku D/MAX-RB X-ray diffraction instrument.
The capacity of lithium ion battery cycle-index table that the present invention mentions is measured by BTS high accuracy battery detection system.
Embodiment 1
Select copper strips as electroplated substrates.
One, copper strips preliminary treatment
Remove oil solution:
The activating recipe and the temperature that during the preparation activated solution, adopt are:
Sulfuric acid 40g/L;
The activation temperature room temperature.
Preprocessing solution is sequentially added in continuous electroplating instrument pre-treatment groove, is heated to assigned temperature.
Two, preparation composite plating solution and anodizing solution
The formula and the condition that during preparation Composite Coatings solution of tin, adopt are:
The oxidation recipes and the condition that during the preparation anodic oxidation solution, adopt are:
Three, it is added in electroplating bath after preparing plating solution, under ultrasonic environment, adopt constant current to electroplate.
Four, copper strips is placed on continuous electric plating device, controls electric current and copper strips translational speed, start to electroplate.
Five, material composite plating obtained carries out anodized in oxidation trough.
Six, by anodic oxidation, complete material is as in tube furnace, and controlling temperature is 280 ℃, and passes into argon gas as protective gas, is incubated 1 hour, obtains the doped meso-porous tin oxide negative material of CNTs of copper substrate.
Embodiment 2
Preparation method: select the copper strips identical with embodiment, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 1 in the solution of electrotinning identical with embodiment 1, after anodic oxidation in the same manner as in Example 1 without heat treatment, directly as lithium ion battery negative material.
Embodiment 3
Preparation method: get copper strips, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 1 in the solution of electrotinning identical with embodiment 1, then adopt heat treatment temperature and the heat treatment time identical with embodiment 1 without anodic oxidation, annealing obtains lithium ion battery negative material.
Performance test
Prepare in the following manner sample, as a comparative example.
Buy natural flake graphite, graphite, PVDF and acetylene black are mixed according to mass ratio 8:1:1, add a certain amount of NMP, stir and make the slurry that viscosity is suitable, employing is scraped the skill in using a kitchen knife in cookery slurry evenly is attached to copper foil surface, makes negative plate.
By embodiment 1, embodiment 2, and the lithium ion battery negative material prepared in embodiment 3 and comparative example is assembled into button cell, and they are carried out to performance test.
The test result of embodiment 1, embodiment 2, embodiment 3 and comparative example is as shown in table 1:
Table 1: specific capacity contrast table after the different materials charge and discharge cycles
As can be seen from Table 1, the present invention has the specific discharge capacity apparently higher than prior art, and simultaneously, after 50 circulations, special capacity fade is only 0.8%, can meet the requirement that service time of battery is long, cycle performance is good.
Embodiment 4
Select copper strips as electroplated substrates.
Seven, copper strips preliminary treatment
Remove oil solution:
The activating recipe and the temperature that during the preparation activated solution, adopt are:
Sulfuric acid 25g/L;
The activation temperature room temperature.
Preprocessing solution is sequentially added in continuous electroplating instrument pre-treatment groove, is heated to assigned temperature.
Eight, preparation composite plating solution and anodizing solution
The formula and the condition that during preparation Composite Coatings solution of tin, adopt are:
The oxidation recipes and the condition that during the preparation anodic oxidation solution, adopt are:
Nine, it is added in electroplating bath after preparing plating solution, under ultrasonic environment, adopt constant current to electroplate.
Ten, copper strips is placed on continuous electric plating device, controls electric current and copper strips translational speed, start to electroplate.
11, material composite plating obtained carries out anodized in oxidation trough.
12, by anodic oxidation, complete material is as in tube furnace, and controlling temperature is 200 ℃, and passes into argon gas as protective gas, is incubated 0.5 hour, obtains the doped meso-porous tin oxide negative material of CNTs of copper substrate.
Embodiment 5
Preparation method: select the copper strips identical with embodiment 4, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 4 in the solution of electrotinning identical with embodiment 4, after anodic oxidation in the same manner as in Example 4 without heat treatment, directly as lithium ion battery negative material.
Embodiment 6
Preparation method: get copper strips, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 4 in the solution of electrotinning identical with embodiment 4, then adopt heat treatment temperature and the heat treatment time identical with embodiment 4 without anodic oxidation, annealing obtains lithium ion battery negative material.
Performance test
Prepare in the following manner sample, as a comparative example.
Buy natural flake graphite, graphite, PVDF and acetylene black are mixed according to mass ratio 8:1:1, add a certain amount of NMP, stir and make the slurry that viscosity is suitable, employing is scraped the skill in using a kitchen knife in cookery slurry evenly is attached to copper foil surface, makes negative plate.
By embodiment 4, embodiment 5, and the lithium ion battery negative material prepared in embodiment 6 and comparative example is assembled into button cell, and they are carried out to performance test.
The test result of embodiment 4, embodiment 5, embodiment 6 and comparative example is as shown in table 2:
Table 2: specific capacity contrast table after the different materials charge and discharge cycles
As can be seen from Table 1, the present invention has the specific discharge capacity apparently higher than prior art, and simultaneously, after 50 circulations, special capacity fade is 3%, can meet the requirement that service time of battery is long, cycle performance is good.
Embodiment 7
Select copper strips as electroplated substrates.
13, copper strips preliminary treatment
Remove oil solution:
The activating recipe and the temperature that during the preparation activated solution, adopt are:
Sulfuric acid 75g/L;
The activation temperature room temperature.
Preprocessing solution is sequentially added in continuous electroplating instrument pre-treatment groove, is heated to assigned temperature.
14, preparation composite plating solution and anodizing solution
The formula and the condition that during preparation Composite Coatings solution of tin, adopt are:
The oxidation recipes and the condition that during the preparation anodic oxidation solution, adopt are:
15, it is added in electroplating bath after preparing plating solution, under ultrasonic environment, adopt constant current to electroplate.
16, copper strips is placed on continuous electric plating device, controls electric current and copper strips translational speed, start to electroplate.
17, material composite plating obtained carries out anodized in oxidation trough.
18, by anodic oxidation, complete material is as in tube furnace, and controlling temperature is 380 ℃, and passes into argon gas as protective gas, is incubated 2 hours, obtains the doped meso-porous tin oxide negative material of CNTs of copper substrate.
Embodiment 8
Preparation method: select the copper strips identical with embodiment 7, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 7 in the solution of electrotinning identical with embodiment 7, after anodic oxidation in the same manner as in Example 7 without heat treatment, directly as lithium ion battery negative material.
Embodiment 9
Preparation method: get copper strips, electroplate the CNTs doping metals tin layer of the material uniform thickness of electroplating in one deck and embodiment 7 in the solution of electrotinning identical with embodiment 7, then adopt heat treatment temperature and the heat treatment time identical with embodiment 7 without anodic oxidation, annealing obtains lithium ion battery negative material.
Performance test
Prepare in the following manner sample, as a comparative example.
Buy natural flake graphite, graphite, PVDF and acetylene black are mixed according to mass ratio 8:1:1, add a certain amount of NMP, stir and make the slurry that viscosity is suitable, employing is scraped the skill in using a kitchen knife in cookery slurry evenly is attached to copper foil surface, makes negative plate.
By embodiment 7, embodiment 8, and the lithium ion battery negative material prepared in embodiment 9 and comparative example is assembled into button cell, and they are carried out to performance test.
The test result of embodiment 7, embodiment 8, embodiment 9 and comparative example is as shown in table 3:
Table 3: specific capacity contrast table after the different materials charge and discharge cycles
As can be seen from Table 1, the present invention has the specific discharge capacity apparently higher than prior art, and simultaneously, after 50 circulations, special capacity fade is 5%, can meet the requirement that service time of battery is long, cycle performance is good.
Claims (9)
1. the doped stannum oxide of the CNTs for a lithium ion battery negative material, it is characterized in that, to have in copper strips substrate surface one side the mesoporous tin oxide film cathode material that CNTs doping proportion is 3.5%～4.5%, the mesoporous tin oxide film that described CNTs doping proportion is 3.5%～4.5% is the metallic tin coating at copper strips substrate surface one side composite plating CNTs Uniform Doped, then form after anodic oxidation and heat treatment.
2. the preparation method of the doped stannum oxide of the CNTs for lithium ion battery negative material claimed in claim 1, is characterized in that, comprises the following steps:
(1) through pretreated copper strips substrate surface one side, adopting the composite plating method to electroplate the tin metal layer of one deck even carbon nanotube doping;
(2) step (1) is electroplated to the gained composite deposite and carry out anodic oxidation, form the stannic oxide layer doped with carbon nano-tube;
(3) step (2) resulting materials is heat-treated.
3. the preparation method of CNTs doped stannum oxide negative material according to claim 2, is characterized in that, the tin metal layer of the described even carbon nanotube doping of step (1), and its thickness is 10～15 μ m.
4. CNT according to claim 2
sthe preparation method of doped stannum oxide negative material, is characterized in that, the pretreatment condition of the described copper strips substrate of step (1) is specific as follows:
1) oil removing
Preparation adopts while removing oil solution remove oil formula and remove oil temperature is:
The oil solution that removes that employing is added each material preparation by above-mentioned quality-volumetric concentration carries out oil removal treatment at 80～90 ℃ to the copper strips substrate;
2) activation
The activating recipe and the activation temperature that during the preparation activated solution, adopt are:
Sulfuric acid 25～75g/L;
The temperature room temperature;
5. CNT according to claim 2
sthe preparation method of doped stannum oxide negative material, is characterized in that, the composite plating condition of the tin metal layer of the described even carbon nanotube doping of step (1) is as follows:
The formula and the condition that during preparation Composite Coatings solution of tin, adopt are:
The copper strips substrate is placed on continuous electric plating device, adopts above-mentioned Composite Coatings solution of tin, control current density, electroplating temperature and electroplating time, electroplate and obtain CNTs doped tin coating.
6. the preparation method of CNTs doped stannum oxide negative material according to claim 2, is characterized in that, after the described anodic oxidation of step (2), in oxide skin(coating), carbon nano-tube proportion is 3.5%～4.5%.
7. CNT according to claim 2
sthe preparation method of doped stannum oxide negative material, is characterized in that, the described anodic oxidation condition of step (2) is as follows:
The oxidation recipes and the condition that during the preparation anodic oxidation solution, adopt are:
The boric acid of amount of calculation is dissolved in the deionized water of institute's dose volume 1/3, then deionized water is added, constantly stir and make its dissolving, after again sodium sulphate being dissolved, add in solution, solution is heated to 25～50 ℃, and carries out magnetic agitation, obtain anodic oxidation solution; The resulting material of step (1) is placed in to the oxidation trough that anodic oxidation solution is housed, controls current density, oxidizing temperature and oxidization time, obtain the CNTs doped tin oxide layer.
8. CNT according to claim 2
sthe preparation method of doped stannum oxide negative material, is characterized in that, the described heat treatment temperature of step (3) is controlled at 200～380 ℃, and the time is 0.5～2 hour, and protective gas is argon gas.
9. CNT according to claim 2
sthe preparation method of doped stannum oxide negative material, is characterized in that, after the described heat treatment of step (3), stannic oxide layer thickness is 10～15 μ m, and mesoporous diameter is 3～10nm.
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