CN105390702A - Foam-nickel-based carbon nano tube doped Sn/SnO/SnO2 layered three-dimensional porous anode material and preparation method thereof - Google Patents
Foam-nickel-based carbon nano tube doped Sn/SnO/SnO2 layered three-dimensional porous anode material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- 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 present invention discloses a foam-nickel-based carbon nano tube doped Sn/SnO/SnO2 layered three-dimensional porous anode material which comprises foam nickel used as a current collector and a carbon nano tube doped Sn/SnO/SnO2 layered porous three-dimensional structure attached to the surface of the foam nickel. The preparation method disclosed by the present invention comprises: firstly, performing surface preprocessing on the foam nickel with a three-dimensional structure; then dispersing processed carbon nano tubes (CNTs) uniformly into tin plated solution; performing composite plating by using the foam nickel as a substrate; then performing anodic oxidation processing on the obtained material; and carrying out vacuum drying. The layered three-dimensional porous lithium ion battery anode material prepared by adopting the method has excellent electrochemical performance, and the first discharged specific capacity reaches 800-1,200m Ah/g, and average coulombic efficiency is kept about 98 percent after 50 times of cycles. The preparation process provided by the present invention is simple, and the prepared anode material has excellent performance and can be industrially produced in a large scale.
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 a kind of nickel foam base carbon nanotube doping Sn/SnO/SnO
2three-dimensional porous negative material of stratiform and preparation method thereof.
Background technology
Lithium ion battery relies on its long circulation life, high-energy-density, low self-discharge characteristic and the advantage such as pollution-free are widely used on the equipment such as mixed power electric car, electric automobile, portable type electronic product, the fast development of these equipment, to energy density, the cycle life of lithium ion battery, fail safe is had higher requirement.Negative material is as one of the core component of lithium ion battery, important impact is had on raising capacity of lithium ion battery and cycle life, business-like negative material is carbon class material at present, its practical application capacity is very close to theoretical capacity (372mAh/g), but capacity is still very little, a kind of negative material of high-energy-density density is looked for become the main target of present material worker as what is the need for.
The oxide of tin relies on the studied person of its high theoretical capacity to think a kind of candidate of most possible replacement carbon negative pole material, its capacity is nearly three times of material with carbon element, receive the extensive concern of various countries researcher at present, but tin material is in repeatedly charge and discharge cycles process, Infix and desfix repeatedly due to lithium ion makes material that huge change in volume occur, easily cause material efflorescence to destroy, cause charge-discharge performance not good.In order to solve the problem, method main at present has to be prepared multicomponent alloy material, material nano and introduction of carbon material and adulterates.
In doping vario-property research, carbon nano-tube is as monodimension nanometer material, not only have outside the nano effect such as skin effect, small-size effect that conventional nano material has, also there is lightweight, hexagonal structure and connect perfect and excellent mechanics, electricity and chemical property.Carbon nano-tube and tin material carry out compound tense, have had great castering action to tin material performance, receive pay close attention to widely in battery material field.If [Y.Wangetal.ChemistryofMaterials.21 (2009) 3210-3215] such as Wang is template with CNTs, the tin base cathode material wrapped up by CNTs has been prepared by chemical vapour deposition technique, this material shows good chemical property, after the charge and discharge cycles of 80 times, its specific capacity still has 526mAh/g, but batch production is had any problem.Uchiyama etc. [H.Uchiyamaetal.ElectrochemCommun.10 (2008) 52-55] have prepared cancellated tin oxide nano monocrystalline in aqueous by hydro thermal method, with the tin negative pole material that the method prepares, its first charge-discharge capacity reaches 900mAh/g.Du etc. [Z.J.Duetal.ElectrochimicaActa.55 (2010) 2527-2541] use the method for chemical plating to be attached to by tin to have on the foam copper of three-D space structure, first discharge specific capacity is 737mAh/g, after 20 circulations, also have the capacity residue of 97%, achieve good cycle performance.
Plating is exactly the process utilizing electrolysis principle to plate other metal or alloy of skim on some metal surface, the technique utilizing electrolysis to make the surface attachment layer of metal film of metal or other material, because of the simple and successful of its technique, so applied to rapidly in industry-by-industry.Composite plating be solia particle is added in plating solution with metal or alloy codeposition, form a kind of process of composite surface material of Metal Substrate, to meet special application requirement, such as strengthen conductivity, resistance to wear, anti-corrosive properties etc.Current many researchers go to prepare lithium ion battery negative material with electro-plating method, and make great progress, Pu etc. [W.H.Puetal.ElectrochimiaActa.50 (2005) 4140-4145] have electroplated tin film with electric plating method at copper foil surface, again in conjunction with Technology for Heating Processing, prepare Sn-Cu alloy material of cathode, average coulombic efficiency reaches 95%, and 50 circulations do not come off, and have good cycle performance.
The selection of the substrate of plating generally has a lot, probably can be divided into two and three dimensions substrate, two dimension substrate has: nickel foil, titanium foil, Copper Foil etc., three-dimensional substrates is exactly the most significantly foam metal (Ni, Cu etc.), it is large that three-dimensional foam metal has specific area, the features such as concrete dynamic modulus, can alleviate the enormousness strain that lithium ion battery material produces in charge and discharge process, thus the cycle performance of reinforcing material.Material in plating can obtain different structures, the material of many layer structures, can not only strengthen the adhesion of coating and substrate, makes coating be not easy to come off in charge and discharge process, improves the cycle performance of material, more can provide outstanding capacity.Tin is electroplated in the tobacco mosaic virus (TMV) (tobaccomosaicvirus) with three-D space structure by Chen etc. [X.L.Chenetal.JournalofPowerSources.211 (2012) 129-132], this 3D negative material presents good circulation ability, also there is after 100 circulations the residual capacity of 560mAh/g, high rate performance is also very excellent, and the selection of visible material is very important on the impact of performance.Tamura etc. [N.Tamuraetal.JournalofPowerSources.107 (2002) 48-55] are in order to strengthen the adhesion of tin coating and Copper Foil substrate, in conjunction with Technology for Heating Processing after plating, the composite bed of tin-copper is generated between tin layers and Copper Foil substrate, with there is no heat treated contrast, after 10 circulations, residual capacity is increased to 94% from 20%, improves the materials'use life-span.
Anodic oxidation to refer to metal or metal alloy in the middle of suitable electrolyte as anode, by anode current, makes anode surface obtain the method be oxidized.Yang etc. [D.Yangetal.JournalofEthnopharmacology.23 (2009) 159-163] are that electrolyte carries out anodic oxidation with ammonium fluoride solution, have obtained Nano tube array of titanium dioxide.Anodic oxidation due to its principle simple, technological requirement is low, is applicable to suitability for industrialized production, is thus widely used in field of surface treatment and other field.
Although had part basis work about the research of tin and oxide cathode material thereof, but the industrialization of distance tin and oxide cathode material thereof still has certain distance, looking for as what is the need for a kind of not only convenient but also effectively can synthesize the method for tin and oxide material thereof, has been the most important thing of present researcher.
Summary of the invention
The object of the invention is the problems such as high for tin oxide negative material cost of the prior art, cycle performance is poor, preparation process is complicated, a kind of nickel foam base carbon nanotube doping Sn/SnO/SnO is provided
2three-dimensional porous negative material of stratiform and preparation method thereof.Proposition as collector, adopts composite plating anode oxidation method prepares carbon nano tube-doped Sn/SnO/SnO by three-dimensional porous material nickel foam
2the negative material of stratiform three-dimensional porous structure, nickel foam porosity is large, can alleviate the change in volume that tin material is huge in charge and discharge process, the carbon nano-tube added contributes to the circulation electric conductivity improving tin material, and the structure of multilevel oxide improves the capacity of material.Special construction, specific capacity are high, stable cycle performance to adopt the negative material prepared of the method to have, and suitability for industrialized is produced.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of nickel foam base carbon nanotube doping Sn/SnO/SnO of the present invention
2the three-dimensional porous negative material of stratiform, comprises nickel foam as collector, and is attached to the carbon nano tube-doped Sn/SnO/SnO on described nickel foam surface
2layered porous three-dimensional structure.
Preferably, the external diameter of described carbon nano-tube is 10 ~ 100nm, and length is 0.5 ~ 10 μm.
Preferably, described nickel foam thickness is 0.5mm, and voidage is 95%.
Preferably, composite plating anode oxidation method prepares described carbon nano tube-doped Sn/SnO/SnO is adopted
2layered porous three-dimensional structure.
Preferably, composite plating anode oxidation method are implemented as: even carbon nanotube be distributed in tin plating solution and obtain composite plating solution of tin; Adopt compound electric plating method at the tin metal coating of nickel foam electroplating surface one deck doped carbon nanometer pipe, composite deposite carries out anodic oxidation.
A kind of nickel foam base carbon nanotube described above doping Sn/SnO/SnO of the present invention
2the preparation method of the three-dimensional porous negative material of stratiform, comprises the steps:
(1) first preliminary treatment is carried out to nickel foam, comprise surface degreasing and activation, then the carbon nano-tube after process is distributed in tin plating solution with the even concentration of 4 ~ 5g/L obtains composite plating solution of tin;
(2) compound electric plating method is adopted to electroplate the tin metal coating of one deck doped carbon nanometer pipe the nickel foam through pre-treatment step (1) gained;
(3) composite deposite of step (2) plating gained is carried out anodic oxidation, the carbon nano tube-doped Sn/SnO/SnO of final formation
2the oxide skin(coating) of stratiform three-dimensional structure;
(4) material of step (3) gained is carried out vacuumize.
Preferably, pretreated oil removing, the activation condition of the nickel foam described in step (1) are specific as follows:
A) oil removing
What configuration adopted when removing oil solution removes oil formula and remove oil temperature is:
B) activate
The activating recipe adopted during configuration activated solution and activation temperature are:
Adopt above oil removing, activating recipe carries out preliminary treatment to nickel foam.
The treatment step of the CNTs of step (1) described process is: by mass concentration be first 18.25% HCl solution add in the beaker containing CNTs, obtain the pretreatment solution that CNTs content is 0.5 ~ 4g/L, again by above-mentioned pretreatment solution ultrasonic vibration, magnetic agitation 5 ~ 24 hours simultaneously, again CNTs is separated from pretreatment solution, finally by CNTs drying 24 hours.
Preferably, in step (2), composite plating solution formula is as follows:
Tin plating solution needs magnetic agitation even after adding carbon nano-tube, then is placed on electroplating device by nickel foam, puts into composite plating solution, electroplates according to above condition, obtain the tin metal coating of doped carbon nanometer pipe.The Chinese name of PVP is: polyvinylpyrrolidone.
Preferably, the combination electrode that step (2) obtains is placed in the groove that anodic oxidation solution is housed, and combination electrode connects positive source, and other metals do reference electrode, carries out anodic oxidation according to following condition to electrode.The formula of anodic oxidation solution is as follows:
Preferably, step (4) vacuum drying temperature is 60 DEG C, and the time is 8-12h.
Finally obtain a kind of foam Ni-based CNTs doping Sn/SnO/SnO
2the negative material of stratiform three-dimensional porous structure.
It is large that three-dimensional foam metal has specific area, the features such as concrete dynamic modulus, can alleviate the enormousness strain that lithium ion battery material produces in charge and discharge process, thus the cycle performance of reinforcing material.The present invention selects nickel foam as collector, the specific area of electrode can greatly be increased, and play certain cushioning effect for active material in the great change of charge and discharge process volume, the efficiency of Lithium-ion embeding and deintercalation can be improved to a certain extent, thus improve the chemical property of electrode.
Carbon nano-tube, as monodimension nanometer material, not only has outside the nano effect such as skin effect, small-size effect that conventional nano material has, also has lightweight, hexagonal structure and connects perfect and excellent mechanics, electricity and chemical property.Carbon nano-tube and tin material carry out compound tense, have had great castering action to tin material performance.The specification of the CNTs that the present invention selects is external diameter 10 ~ 100nm, and length is 0.5 ~ 10 μm, is that external diameter is less, and electric conductivity is better, and in conjunction with CNTs cost, prioritizing selection external diameter is 10 ~ 20nm because CNTs external diameter is when below 30nm.
The present invention adopts hydrochloric acid to CNTs process, is conducive to reducing carbon dust residual in CNTs preparation process or other impurity, and passes through the CNTs structural integrity of HCl treatment, can play himself performance to greatest extent.
Plating is exactly the process utilizing electrolysis principle to plate other metal or alloy of skim on some metal surface, the technique utilizing electrolysis to make the surface attachment layer of metal film of metal or other material, because of the simple and successful of its technique, so applied to rapidly in industry-by-industry.Composite plating be solia particle is added in plating solution with metal or alloy codeposition, form a kind of process of composite surface material of Metal Substrate, to meet special application requirement, such as strengthen conductivity, resistance to wear, anti-corrosive properties etc.In the tin oxide layer of the present invention's oxidation, CNTs can be evenly distributed on whole negative active core-shell material part, and part CNTs is through between oxide skin(coating), and due to the conductive capability of CNTs excellence, the speed that electronics is moved in active material strengthens greatly.
Anodic oxidation to refer to metal or metal alloy in the middle of suitable electrolyte as anode, by anode current, makes anode surface obtain the method be oxidized.Anodic oxidation due to its principle simple, technological requirement is low, is applicable to suitability for industrialized production.The present invention adopts anodised method, can obtain Sn/SnO/SnO
2stratiform three-dimensional porous structure, can provide more capacity, and more stable chemical property, then in conjunction with the three-D space structure of nickel foam, can alleviate the bulk strain of electrode material in charge and discharge process, make material have better stability.
The material of many layer structures, can not only strengthen the adhesion of coating and substrate, makes coating be not easy to come off in charge and discharge process, improves the cycle performance of material, more can provide outstanding capacity.The foam that the present invention prepares Ni-based CNTs doping Sn/SnO/SnO
2it is high that the three-dimensional porous negative material of stratiform has charging and discharging capacity, the advantage of good cycle.A kind of foam that the present invention prepares Ni-based CNTs doping Sn/SnO/SnO
2stratiform three-dimensional porous negative material first charge-discharge specific capacity is 830 ~ 1200mAh/g, also has excellent cycle performance and outstanding coulombic efficiency simultaneously, and also have 400mAh/g after 50 circulations, average coulombic efficiency remains on about 98%.This is the result because following 3 factors produce: 1, CNTs runs through between collector and active material, the conductivity that CNTs is good and mechanical performance, good skeleton function can be directly played at active material and collector, reduce the efflorescence of active material in charge and discharge process and come off, the cycle performance of reinforcing material.2, nickel foam is as collector, because be porous three-dimensional material, high porosity and large specific area, can alleviate the enormousness that Lithium-ion embeding and deintercalation cause to a great extent and change, promote the stability of material.3, adopt anodised method, prepare and there is CNTs doping Sn/SnO/SnO
2stratiform three-dimensional porous structure negative material, can not only improve charging and discharging capacity, can also reduce change in volume.
Compared with other inventive methods, the present invention possesses following outstanding advantage:
1, the doping of carbon nano-tube improves conductivity, simultaneously the cycle performance of reinforcing material, and the capacity attenuation after circulating is reduced; 2, anode oxidation method preparation has Sn/SnO/SnO
2the negative material of stratiform three-dimensional porous structure, method is simple, and practical, production cost is low; 3, practical non-cyanide solution is electroplating solution, and environmentally safe, meets environmental requirement; 4, production cost is lower, and preparation process is simple.
A kind of nickel foam base carbon nanotube doping of the present invention Sn/SnO/SnO
2the surface topography of the three-dimensional porous negative material of stratiform is measured (FE-SEM, S-4800, Hitachi, Japan) by scanning electron microscopy.
A kind of nickel foam base carbon nanotube doping of the present invention Sn/SnO/SnO
2the thing of the three-dimensional porous negative material of stratiform is measured by XRD method mutually.
The capacity of lithium ion battery cycle-index that the present invention mentions is measured by BTS high accuracy battery test macro.
Accompanying drawing explanation
Fig. 1 is nickel foam base carbon nanotube of the present invention doping Sn/SnO/SnO
2the preparation flow schematic diagram of the three-dimensional porous negative material of stratiform;
Fig. 2 schemes without the SEM of the nickel foam metal of any process in embodiment 1;
Fig. 3 is the nickel foam base carbon nanotube doping Sn/SnO/SnO of electroplating time 300s oxidization time 200s
2the SEM figure of the three-dimensional porous negative material of stratiform;
The nickel foam base carbon nanotube doping Sn/SnO/SnO of Fig. 4 to be electroplating time 300s oxidization time be 200s
2the X-ray diffractogram of the three-dimensional porous negative material of stratiform;
Fig. 5 is plating 300s oxidation 200s nickel foam base carbon nanotube doping Sn/SnO/SnO
2the cycle performance figure of the three-dimensional porous negative material of stratiform;
Fig. 6 is for being oxidized 250s nickel foam base carbon nanotube doping Sn/SnO/SnO for plating 300s
2the cycle performance figure of the three-dimensional porous negative material of stratiform;
Fig. 7 is plating 700s oxidation 200s nickel foam base carbon nanotube doping Sn/SnO/SnO
2the cycle performance figure of the three-dimensional porous negative material of stratiform.
Embodiment
By following examples the present invention will be described in more detail explain, but scope is not limited to the scope of following examples.
Embodiment 1:
Select nickel foam as electroplated substrates.Fig. 1 is preparation flow schematic diagram of the present invention, and Fig. 2 schemes without the SEM of the nickel foam metal of any process.
(1) nickel foam preliminary treatment
Oil removal treatment, solution allocation is as follows:
Carry out activation processing again, solution allocation is as follows
(2) carry out removal of impurities and dispersion treatment to CNTs, selection external diameter is 10 ~ 20nm, and length is 1 ~ 3 μm of carbon nano-tube.First by mass concentration be 18.25% HCl solution add in the container containing CNTs, obtain the pretreatment solution that CNTs content is 2g/L;
Again by above-mentioned pretreatment solution ultrasonic vibration, magnetic agitation 5 ~ 24 hours simultaneously, then CNTs is separated from pretreatment solution, finally by CNTs drying 24 hours.
(3) composite plating solution and anodic oxidation solution is prepared
Above-mentioned process being crossed the CNTs obtained joins in tin plating solution with the amount of 4g/L, and magnetic agitation 8 ~ 12 hours makes CNTs evenly spread in tin plating solution, and formula and the condition of preparing zinc-plated composite solution are as follows:
(4) nickel foam is put into the composite plating bath solution prepared, electroplating time is respectively 300,500,700,900,1100 and 1300s, obtained composite plating sample.
(5) put in oxidizing solution by the sample that composite plating obtains, carry out anodized, the anodised time is respectively 200,300 and 400s, and the formula of anodic oxidation solution is as follows:
(6) to the foam Ni-based CNTs doping Sn/SnO/SnO that step (5) obtains
2the three-dimensional porous negative material of stratiform vacuumize 8-12 hour under the environment of 60 DEG C obtains negative electrode material sample.
Fig. 3 is the foam Ni-based CNTs doping Sn/SnO/SnO that plating 300s is oxidized 200s
2the SEM figure of the three-dimensional porous negative material of stratiform, after adding CNTs, have the CNTs of wire to be attached in foam nickel base, the oxide particle on surface becomes porosity and looseness.
Fig. 4 is nickel foam base carbon nanotube doping Sn/SnO/SnO
2the XRD figure of the three-dimensional porous negative material of stratiform, has obtained C, Ni, Sn, Sn from figure
4+, Sn
2+thing exist mutually.
Adulterate the CNTs obtained Sn/SnO/SnO
2stratiform three-dimensional porous negative material assembling simulation button cell carries out performance test.The negative material of different conditions step (6) obtained with slitter carries out cut-parts, and the negative plate obtained with cut-parts is negative pole, and lithium metal is electrode as a comparison, and in argon gas atmosphere glove box, assemble the button cell of 2025, electrolyte is the LiPF of 1mol/L
6, diaphragm is Celgard2400 type.Charge-discharge test carries out in room temperature, and instrument is new prestige battery test system, and test voltage scope is 0.01 ~ 3.0V, and measuring current is 0.1C, obtains the chemical property of the sample of different electroplating time and different oxidization time, and its test result is as shown in table 1.
Table 1: different electroplating time and oxidization time sample chemical property contrast table
As can be seen from Table 1, the sample chemical property that different electroplating time and oxidization time obtain is different, electroplating time is different, cause thickness of coating just different, electroplating time is oversize, thickness of coating is too thick, easily causes material be connected loosely with base in the circulating cycle and come off, and the chemical property of material is deteriorated.
Embodiment 2
In conjunction with the embodiments 1, select electroplating time 300s oxidization time 200s to do laboratory sample, all the other steps are identical with embodiment 1.Adopt traditional lithium-ion battery method of testing, the first charge-discharge specific capacity obtaining this negative pole active principle is 1260mAh/g, and also have 393.4mAh/g after 50 circulations, average coulombic efficiency reaches 98%, and its cycle performance as shown in Figure 5.
Embodiment 3
In conjunction with the embodiments 1, select electroplating time 300s oxidization time 250s to do laboratory sample, all the other steps are identical with embodiment 1.Adopt traditional lithium-ion battery method of testing, the first charge-discharge specific capacity obtaining this negative pole active principle is 912mAh/g, and after 60 circulations, residual capacity is 288mAh/g, and average coulombic efficiency is about 97%, stable cycle performance, its cycle performance as shown in Figure 6.
Embodiment 4
In conjunction with the embodiments 1, select electroplating time 700s oxidization time 200s to do laboratory sample, all the other steps are identical with embodiment 1.Adopt traditional lithium-ion battery method of testing, the first charge-discharge specific capacity obtaining this negative pole active principle is 837mAh/g, after 50 circulations, residual capacity is only less than 100mAh/g, but average coulombic efficiency still remains on about 97%, and its cycle performance figure as shown in Figure 7.
Comparative example 2,3 and 4, different electroplating time can be obtained and the performance of oxidization time on material has different impacts, electroplating time is oversize, cause active principle layer too thick, easy powder of detached in cycle charge discharge electric process, thus causing material electrochemical performance to be deteriorated, suitable plating and the performance of the selection of time of oxidation on material have very important impact.
Claims (10)
1. a nickel foam base carbon nanotube doping Sn/SnO/SnO
2the three-dimensional porous negative material of stratiform, comprises nickel foam as collector, and is attached to the carbon nano tube-doped Sn/SnO/SnO on described nickel foam surface
2layered porous three-dimensional structure.
2. nickel foam base carbon nanotube doping Sn/SnO/SnO as claimed in claim 1
2the three-dimensional porous negative material of stratiform, is characterized in that, the external diameter of described carbon nano-tube is 10 ~ 100nm, and length is 0.5 ~ 10 μm.
3. nickel foam base carbon nanotube doping Sn/SnO/SnO as claimed in claim 1
2the three-dimensional porous negative material of stratiform, is characterized in that, described nickel foam thickness is 0.5mm, and voidage is 95%.
4. nickel foam base carbon nanotube doping Sn/SnO/SnO as claimed in claim 1
2the three-dimensional porous negative material of stratiform, is characterized in that, adopts composite plating anode oxidation method prepares described carbon nano tube-doped Sn/SnO/SnO
2layered porous three-dimensional structure.
5. nickel foam base carbon nanotube doping Sn/SnO/SnO as claimed in claim 1
2the three-dimensional porous negative material of stratiform, is characterized in that, composite plating anode oxidation method are implemented as: even carbon nanotube be distributed in tin plating solution and obtain composite plating solution of tin; Adopt compound electric plating method at the tin metal coating of nickel foam electroplating surface one deck doped carbon nanometer pipe, composite deposite carries out anodic oxidation.
6. the nickel foam base carbon nanotube doping Sn/SnO/SnO as described in any one of claim 1-5
2the preparation method of the three-dimensional porous negative material of stratiform, comprises the steps:
(1) first preliminary treatment is carried out to nickel foam, comprise surface degreasing and activation, then the carbon nano-tube after process is distributed in tin plating solution with the even concentration of 4 ~ 5g/L obtains composite plating solution of tin;
(2) compound electric plating method is adopted to electroplate the tin metal coating of one deck doped carbon nanometer pipe the nickel foam through pre-treatment step (1) gained;
(3) composite deposite of step (2) plating gained is carried out anodic oxidation, the carbon nano tube-doped Sn/SnO/SnO of final formation
2the oxide skin(coating) of stratiform three-dimensional structure;
(4) material of step (3) gained is carried out vacuumize.
7. preparation method according to claim 6, is characterized in that, pretreated oil removing, the activation condition of the nickel foam described in step (1) are specific as follows:
A) oil removing
What configuration adopted when removing oil solution removes oil formula and remove oil temperature is:
B) activate
The activating recipe adopted during configuration activated solution and activation temperature are:
Adopt above oil removing, activating recipe carries out preliminary treatment to nickel foam.
8. preparation method according to claim 6, is characterized in that, the composite plating solution formula of step (2) is as follows
Tin plating solution needs magnetic agitation even after adding carbon nano-tube, then is placed on electroplating device by nickel foam, puts into composite plating solution, electroplates according to above condition, obtain the tin metal coating of doped carbon nanometer pipe.
9. preparation method according to claim 6, is characterized in that, formula and the reaction condition of the anodic oxidation solution of step (3) are as follows:
The combination electrode that step (2) obtains is placed in the groove that anodic oxidation solution is housed, according to above condition, carries out anodic oxidation.
10. preparation method according to claim 6, is characterized in that, step (4) vacuum drying temperature is 60 DEG C, and the time is 8-12h.
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| CN107316975A (en) * | 2017-07-26 | 2017-11-03 | 清华大学深圳研究生院 | A kind of sodium-ion battery negative plate |
| CN108365207A (en) * | 2018-03-27 | 2018-08-03 | 北京化工大学 | A kind of negative electrode of lithium ion battery stannous oxide/carbon composite and its synthetic method |
| CN108807015A (en) * | 2018-06-24 | 2018-11-13 | 湖南科技大学 | A kind of in-situ preparation method of electrochemical capacitor electrode piece and its application |
| CN109301249A (en) * | 2018-08-29 | 2019-02-01 | 济南大学 | A kind of nickel foam original position load SnO2Nanoparticle doped graphitic carbon composite material and preparation method thereof and application |
| CN112042668A (en) * | 2020-09-17 | 2020-12-08 | 中国农业大学 | Application of multi-walled carbon nanotubes in inhibition of tobacco mosaic virus infection |
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| US11559791B2 (en) * | 2020-01-22 | 2023-01-24 | The Regents Of The University Of California | Carbon-doped nickel oxide catalyst and methods for making and using thereof |
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| CN106058189A (en) * | 2016-07-19 | 2016-10-26 | 天津师范大学 | Method for synthesizing high-capacity anode material of lithium ion battery |
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| CN108365207A (en) * | 2018-03-27 | 2018-08-03 | 北京化工大学 | A kind of negative electrode of lithium ion battery stannous oxide/carbon composite and its synthetic method |
| CN108365207B (en) * | 2018-03-27 | 2021-01-19 | 北京化工大学 | Lithium ion battery cathode stannous oxide/carbon composite material and synthesis method thereof |
| CN108807015A (en) * | 2018-06-24 | 2018-11-13 | 湖南科技大学 | A kind of in-situ preparation method of electrochemical capacitor electrode piece and its application |
| CN109301249A (en) * | 2018-08-29 | 2019-02-01 | 济南大学 | A kind of nickel foam original position load SnO2Nanoparticle doped graphitic carbon composite material and preparation method thereof and application |
| CN109301249B (en) * | 2018-08-29 | 2021-05-14 | 济南大学 | Foamed nickel in-situ loaded SnO2Preparation method and application of nano particle doped graphite carbon composite material |
| US11559791B2 (en) * | 2020-01-22 | 2023-01-24 | The Regents Of The University Of California | Carbon-doped nickel oxide catalyst and methods for making and using thereof |
| CN112042668A (en) * | 2020-09-17 | 2020-12-08 | 中国农业大学 | Application of multi-walled carbon nanotubes in inhibition of tobacco mosaic virus infection |
| CN113809300A (en) * | 2021-09-17 | 2021-12-17 | 山东省科学院新材料研究所 | Three-dimensional double-layer structure cathode material of lithium metal battery and preparation method thereof |
| CN114551833A (en) * | 2022-02-23 | 2022-05-27 | 安徽师范大学 | Coral-shaped tin dioxide @ carbon composite nanomaterial and preparation method thereof, semi-solid negative electrode slurry and semi-solid lithium ion battery |
| CN114551833B (en) * | 2022-02-23 | 2023-11-03 | 安徽师范大学 | Coral-morphology tin dioxide@carbon composite nanomaterial and preparation method thereof, semi-solid negative electrode slurry and semi-solid lithium ion battery |
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