CN105390702B - A kind of nickel foam base carbon nanotube doping Sn/SnO/SnO2Three-dimensional porous negative electrode material of stratiform and preparation method thereof - Google Patents

A kind of nickel foam base carbon nanotube doping Sn/SnO/SnO2Three-dimensional porous negative electrode material of stratiform and preparation method thereof Download PDF

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CN105390702B
CN105390702B CN201510915122.8A CN201510915122A CN105390702B CN 105390702 B CN105390702 B CN 105390702B CN 201510915122 A CN201510915122 A CN 201510915122A CN 105390702 B CN105390702 B CN 105390702B
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nickel foam
stratiform
carbon nanotube
negative electrode
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CN105390702A (en
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马增胜
张晶
雷维新
邹幽兰
潘勇
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Xiangtan University
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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
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of nickel foam base carbon nanotubes to adulterate Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform, including nickel foam is as collector, and is attached to the carbon nano tube-doped Sn/SnO/SnO of the foam nickel surface2Layered porous three-dimensional structure.The present invention first carries out surface preparation to the nickel foam with three-dimensional structure, then by treated, carbon nanotube (CNTs) is uniformly distributed in tin plating solution, composite plating is carried out by substrate of nickel foam, then anodized is carried out to resulting material, by vacuum drying.The three-dimensional porous lithium ion battery negative material of stratiform prepared using this method has excellent chemical property, and first discharge specific capacity reaches 800 ~ 1200 mAh/g, and average coulombic efficiency maintains 98% or so after 50 circulations.Preparation process of the invention is simple, and the negative electrode material of preparation is had excellent performance, and can carry out large-scale industrialized production.

Description

A kind of nickel foam base carbon nanotube doping Sn/SnO/SnO2The three-dimensional porous cathode material of stratiform Material and preparation method thereof
Technical field
The invention belongs to lithium ion battery manufacturing field, it is related to a kind of lithium ion battery negative material and preparation method thereof, In particular to a kind of nickel foam base carbon nanotube adulterates Sn/SnO/SnO2Three-dimensional porous negative electrode material of stratiform and preparation method thereof.
Background technique
Lithium ion battery rely on its long circulation life, high-energy density, low self-discharge characteristic and it is pollution-free the advantages that It is widely used in the equipment such as mixed power electric car, electric car, portable electronic product, the quick hair of these equipment Exhibition, energy density, cycle life to lithium ion battery, more stringent requirements are proposed for safety.Negative electrode material is as lithium ion One of core component of battery has important influence to capacity of lithium ion battery and cycle life is improved, commercially at present The negative electrode material of change is Carbon materials, and practical application capacity is very close to theoretical capacity (372mAh/g), but capacity still very little, It such as what is the need for and look for a kind of negative electrode material of high-energy-density density as the main target of present material worker.
The oxide of tin is considered a kind of by researcher by its high theoretical capacity and most possibly replaces carbon negative pole material Candidate, capacity is nearly three times of carbon material, has been now subjected to the extensive concern of various countries researcher, but tin material is more During secondary charge and discharge cycles, since the insertion repeatedly and deintercalation of lithium ion make material that huge volume change occur, it is easy It causes material dusting to destroy, causes charge-discharge performance bad.To solve the above-mentioned problems, main method has preparation at present Multicomponent alloy material, material nano and introduction carbon material are doped.
In doping vario-property research, carbon nanotube not only there is conventional nano material to be had as monodimension nanometer material The nano effects such as skin effect, small-size effect outside, also have light-weight, hexagonal structure connection perfect and excellent power , electricity and chemical property.Carbon nanotube and tin material carry out compound tense, have great castering action to tin material performance, It is had received widespread attention in battery material field.Such as Wang [Y. Wang et al. Chemistry of Materials. 21 (2009) 3210-3215] using CNTs as template, it has been prepared by chemical vapour deposition technique by CNTs packet The tin base cathode material wrapped up in, the material show good chemical property, after 80 charge and discharge cycles, compare Capacity still has 526mAh/g, but batch production is had any problem.[the H. Uchiyama et al. Electrochem such as Uchiyama Commun. 10 (2008) 52-55] it is prepared for the tin oxide nano monocrystalline of reticular structure in aqueous solution with hydro-thermal method, with this The tin negative pole material that method prepares, first charge-discharge capacity have reached 900mAh/g.[the Z. J. Du et al. such as Du Electrochimica Acta. 55 (2010) 2527-2541] tin is attached to three-dimensional space with the method for chemical plating On the foam copper of structure, first discharge specific capacity is 737 mAh/g, and it is remaining that there are also 97% capacity after 20 circulations, is obtained Good cycle performance.
Plating is exactly to plate the process of the other metal or alloy of a thin layer on certain metal surfaces using electrolysis principle, is The technique for making attachment layer of metal film in the surface of metal or other materials product using electrolysis, because of its simple process and effect Obviously, so by applying in various industries rapidly.Composite plating is that solia particle is added in plating solution to be total to metal or alloy Deposition, forms a kind of process of the composite surface material of Metal Substrate, to meet special application requirement, such as enhancing electric conductivity, Wearability, anti-corrosive properties etc..Current many researchers are gone to prepare lithium ion battery negative material with electro-plating method, and are achieved very Big progress, Pu etc. [50 (2005) 4140-4145 of W. H. Pu et al. Electrochimia Acta.] plating Tin film has been electroplated in copper foil surface in method, in conjunction with heat treatment process, is prepared for Sn-Cu alloy material of cathode, average coulomb effect Rate reaches 95%, and 50 times circulation is not fallen off, and has good cycle performance.
The selection of the substrate of plating generally has very much, can probably be divided into two and three dimensions substrate, and two-dimentional substrate has: nickel Foil, titanium foil, copper foil etc., three-dimensional substrates are most significantly exactly foam metal (Ni, Cu etc.), and three-dimensional foam metal has specific surface area Greatly, the features such as porous, can alleviate the enormousness strain that lithium ion battery material generates in charge and discharge process, to increase The cycle performance of strong material.Material in plating can obtain different structures, and the material of more layer structures can not only enhance plating The binding force of layer and substrate, keeps coating not easy to fall off in charge and discharge process, improves the cycle performance of material, be more capable of providing Outstanding capacity.[the X. L. Chen et al. Journal of Power Sources. 211 (2012) such as Chen 129-132] tin is electroplated in the tobacco mosaic virus (TMV) (tobacco mosaic virus) with three-D space structure, it is this 3D negative electrode material presents good circulation ability, also has the residual capacity of 560 mAh/g, high rate performance after 100 circulations Also very excellent, it is seen that influence of the selection of material to performance is critically important.[the N. Tamura et al. such as Tamura 107 (2002) 48-55 of Journal of Power Sources.] in order to enhance the binding force of tin coating Yu copper foil substrate, electricity Heat treatment process is combined after plating, tin-copper composite layer is generated between tin layers and copper foil substrate, with pair not being heat-treated Than residual capacity increases to 94% from 20% after 10 circulations, improves the materials'use service life.
Anodic oxidation refers in suitable electrolyte using metal or metal alloy as anode, passes through anode electricity Stream, the method for aoxidizing anode surface.[the D. Yang et al. Journal of such as Yang Ethnopharmacology. 23 (2009) 159-163] using ammonium fluoride solution as electrolyte progress anodic oxidation, it has been made two Titania nanotube array.Since its principle is simple, technique requires low, suitable industrialized production for anodic oxidation, thus on surface Process field and other fields are widely used.
Although the research about tin and its oxide cathode material has had part basis work, apart from tin and its oxygen The industrialization of compound negative electrode material still has a certain distance, such as what is the need for look for it is a kind of not only facilitate but also can effectively synthesize tin and The method of its oxide material has been the most important thing of present researcher.
Summary of the invention
The purpose of the present invention is for oxidation tin negative pole material in the prior art is at high cost, poor circulation, prepared The problems such as journey is complicated provides a kind of nickel foam base carbon nanotube doping Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform and its Preparation method.It is proposed uses three-dimensional porous material nickel foam as collector, prepares carbon using composite plating and anode oxidation method Nanotube adulterates Sn/SnO/SnO2The negative electrode material of stratiform three-dimensional porous structure, nickel foam porosity is big, can alleviate tin material The huge volume change in charge and discharge process, the carbon nanotube of addition helps to improve the circulation electric conductivity of tin material, more The structure of layer oxide improves the capacity of material.There is special construction, specific capacity using the negative electrode material that this method is prepared High, stable cycle performance, and be suitable for industrialized production.
To achieve the goals above, technical scheme is as follows:
A kind of nickel foam base carbon nanotube of the invention adulterates Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform, including Nickel foam is as collector, and is attached to the carbon nano tube-doped Sn/SnO/SnO of the foam nickel surface2Layered porous three-dimensional Structure.
Preferably, the outer diameter of the carbon nanotube is 10 ~ 100 nm, and length is 0.5 ~ 10 μm.
Preferably, the nickel foam is with a thickness of 0.5 mm, voidage 95%.
Preferably, the carbon nano tube-doped Sn/SnO/SnO is prepared using composite plating and anode oxidation method2Stratiform Porous three-dimensional structure.
Preferably, composite plating and anode oxidation method specific implementation are as follows: carbon nanotube is evenly spread into tin plating solution In obtain composite plating solution of tin；Tin metal using compound electric plating method in one layer of doped carbon nanometer pipe of nickel foam electroplating surface is plated Layer, composite deposite carry out anodic oxidation.
One kind of the invention nickel foam base carbon nanotube described above adulterates Sn/SnO/SnO2The three-dimensional porous cathode of stratiform The preparation method of material, includes the following steps:
(1) first nickel foam is pre-processed, including surface degreasing and activation, then will treated carbon nanotube with 4 ~ 5 The even concentration of g/L, which is distributed in tin plating solution, obtains composite plating solution of tin；
(2) one layer of doped carbon nanometer pipe will be electroplated using compound electric plating method by pre-treatment step (1) resulting nickel foam Tin metal coating；
(3) resulting composite deposite is electroplated in step (2) and carries out anodic oxidation, ultimately form carbon nano tube-doped Sn/ SnO/SnO2The oxide skin(coating) of stratiform three-dimensional structure；
(4) step (3) resulting material is dried in vacuo.
Preferably, the pretreated oil removing of nickel foam described in step (1), activation condition are specific as follows:
A) oil removing
What is used when configuration is except oil solution removes oil formula and except oil temperature are as follows:
B) it activates
The activating recipe and activation temperature used when configuring activated solution are as follows:
Oil removing, activating recipe more than pre-process nickel foam.
The processing step of the CNTs of step (1) described processing are as follows: first contain the HCl solution addition that mass concentration is 18.25% Have in the beaker of CNTs, obtains the pretreatment solution that CNTs content is 0.5 ~ 4 g/L, then above-mentioned pretreatment solution ultrasound is shaken It swings, while magnetic agitation 5 ~ 24 hours, then CNTs is separated from pretreatment solution, it is finally that CNTs is 24 hours dry.
Preferably, in step (2), composite plating solution formula is as follows:
Tin plating solution needs magnetic agitation uniform after carbon nanotube is added, then nickel foam is placed on electroplating device, puts Enter in composite plating solution, be electroplated according to conditions above, obtains the tin metal coating of doped carbon nanometer pipe.The Chinese name of PVP It is: polyvinylpyrrolidone.
Preferably, the combination electrode that step (2) obtains is placed in the slot equipped with anodic oxidation solution, combination electrode connects electricity Source anode, other metals do reference electrode, carry out anodic oxidation to electrode according to the following conditions.The formula of anodic oxidation solution is such as Under:
Preferably, step (4) vacuum drying temperature is 60 DEG C, and the time is 8-12 h.
Finally obtain a kind of Ni-based CNTs doping Sn/SnO/SnO of foam2The negative electrode material of stratiform three-dimensional porous structure.
Three-dimensional foam metal has the features such as large specific surface area, porous, can alleviate lithium ion battery material in charge and discharge The enormousness strain generated in electric process, thus the cycle performance of reinforcing material.The present invention selects nickel foam as collector, The specific surface area of electrode can greatly be increased, and play certain buffering in the great change of charge and discharge process volume for active material Effect can improve the efficiency of lithium ion insertion and deintercalation, to improve the chemical property of electrode to a certain extent.
Carbon nanotube not only has skin effect, small size possessed by conventional nano material as monodimension nanometer material Outside the nano effects such as effect, also there is perfect light-weight, hexagonal structure connection and excellent mechanics, electricity and chemically Energy.Carbon nanotube and tin material carry out compound tense, have great castering action to tin material performance.The CNTs that the present invention selects Specification be 10 ~ 100 nm of outer diameter, length be 0.5 ~ 10 μm, be because CNTs outer diameter in 30 nm or less, outer diameter is smaller, leads Electrical property is better, in conjunction with CNTs cost, preferentially selects outer diameter for 10 ~ 20 nm.
The present invention is handled CNTs using hydrochloric acid, advantageously reduce in CNTs preparation process remaining carbon dust or other Impurity, and pass through the CNTs structural integrity of HCl treatment, its own performance can be played to greatest extent.
Plating is exactly to plate the process of the other metal or alloy of a thin layer on certain metal surfaces using electrolysis principle, is The technique for making attachment layer of metal film in the surface of metal or other materials product using electrolysis, because of its simple process and effect Obviously, so by applying in various industries rapidly.Composite plating is that solia particle is added in plating solution to be total to metal or alloy Deposition, forms a kind of process of the composite surface material of Metal Substrate, to meet special application requirement, such as enhancing electric conductivity, Wearability, anti-corrosive properties etc..CNTs can be evenly distributed on entire negative electrode active material part in the tin oxide layer that the present invention aoxidizes, Part CNTs is through between oxide skin(coating), due to the conductive capability that CNTs is excellent, so that electronics migrated in active material Rate greatly enhances.
Anodic oxidation refers in suitable electrolyte using metal or metal alloy as anode, passes through anode electricity Stream, the method for aoxidizing anode surface.Since its principle is simple, technique requires low, suitable industrialized production for anodic oxidation. The method that the present invention uses anodic oxidation, can obtain Sn/SnO/SnO2Stratiform three-dimensional porous structure is capable of providing more appearances Amount, and more stable chemical property can alleviate electrode material in charge and discharge in conjunction with the three-D space structure of nickel foam Bulk strain in the process makes material have more preferably stability.
The material of more layer structures can not only enhance the binding force of coating and substrate, make coating in charge and discharge process It is not easy to fall off, the cycle performance of material is improved, outstanding capacity is more capable of providing.The foam that the present invention prepares is Ni-based CNTs adulterates Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform has the advantages of charging and discharging capacity is high, good cycle.This Invent a kind of Ni-based CNTs doping Sn/SnO/SnO of the foam prepared2The three-dimensional porous negative electrode material first charge-discharge ratio of stratiform Capacity is 830 ~ 1200 mAh/g, while also having excellent cycle performance and coulombic efficiency outstanding, after 50 circulations There are also 400 mAh/g, average coulombic efficiency is maintained at 98% or so.This is because the result that following three points factor generates: 1, CNTs Between collector and active material, the good electric conductivity of CNTs and mechanical performance can be straight with collector in active material It picks up good skeleton function, reduces in charge and discharge process the dusting of active material and fall off, the cycle performance of reinforcing material. 2, nickel foam is as collector, because being porous three-dimensional material, high porosity and big specific surface area can be very Alleviate lithium ion insertion in big degree to change with enormousness caused by deintercalation, promotes the stability of material.3, using anodic oxygen The method of change is prepared and adulterates Sn/SnO/SnO with CNTs2Stratiform three-dimensional porous structure negative electrode material, can not only improve Charging and discharging capacity, moreover it is possible to reduce volume change.
Compared with other inventive methods, the present invention has advantage following prominent:
1, the doping of carbon nanotube improves electric conductivity, while the cycle performance of reinforcing material, so that the capacity after circulation Decaying reduces；2, anodizing preparation has Sn/SnO/SnO2The negative electrode material of stratiform three-dimensional porous structure, method is simple, Practical, production cost is low；3, practical non-cyanide solution is electroplating solution, and no pollution to the environment meets environmental requirement；4, Lower production costs, preparation process are simple and easy.
A kind of nickel foam base carbon nanotube of the present invention adulterates Sn/SnO/SnO2The surface shape of the three-dimensional porous negative electrode material of stratiform Looks are that (FE-SEM, S-4800, Hitachi, Japan) is measured by scanning electron microscope.
A kind of nickel foam base carbon nanotube of the present invention adulterates Sn/SnO/SnO2The object of the three-dimensional porous negative electrode material of stratiform is mutually It is measured by XRD method.
The capacity of lithium ion battery cycle-index that the present invention mentions is measured by BTS high accuracy battery test macro.
Detailed description of the invention
Fig. 1 is that nickel foam base carbon nanotube of the present invention adulterates Sn/SnO/SnO2The preparation of the three-dimensional porous negative electrode material of stratiform Flow diagram；
Fig. 2 is to scheme in embodiment 1 without the SEM of the nickel foam metal of any processing；
The nickel foam base carbon nanotube that Fig. 3 is 300 s oxidization time of electroplating time, 200 s adulterates Sn/SnO/SnO2Stratiform The SEM of three-dimensional porous negative electrode material schemes；
Fig. 4 is the nickel foam base carbon nanotube doping Sn/SnO/SnO that electroplating time 300s oxidization time is 200 s2Layer The X-ray diffractogram of the three-dimensional porous negative electrode material of shape；
Fig. 5 is that 300 s of plating aoxidize 200 s nickel foam base carbon nanotubes doping Sn/SnO/SnO2Stratiform is three-dimensional porous negative The cycle performance figure of pole material；
Fig. 6 is that 300 s of plating aoxidize 250 s nickel foam base carbon nanotubes doping Sn/SnO/SnO2Stratiform is three-dimensional porous The cycle performance figure of negative electrode material；
Fig. 7 is that 700 s of plating aoxidize 200 s nickel foam base carbon nanotubes doping Sn/SnO/SnO2Stratiform is three-dimensional porous negative The cycle performance figure of pole material.
Specific embodiment
By following embodiment, the present invention will be described in more detail explains, but the scope of the present invention does not limit to In the range of following embodiment.
Embodiment 1:
Select nickel foam as electroplated substrates.Fig. 1 is preparation flow schematic diagram of the invention, and Fig. 2 is without any place The SEM of the nickel foam metal of reason schemes.
(1) nickel foam pre-processes
Oil removal treatment, solution allocation are as follows:
It is activated again, solution allocation is as follows
(2) removal of impurities and decentralized processing are carried out to CNTs, selects outer diameter for 10 ~ 20 nm, length is 1 ~ 3 μm of carbon nanotube.It is first First the HCl solution that mass concentration is 18.25% is added in the container containing CNTs, obtains the pre-treatment that CNTs content is 2 g/L Solution；
Again by above-mentioned pretreatment solution ultrasonic vibration, while magnetic agitation 5 ~ 24 hours, then by CNTs from pretreatment solution Middle separation, it is finally that CNTs is 24 hours dry.
(3) composite plating solution and anodic oxidation solution are prepared
Above-mentioned processed obtained CNTs is added in tin plating solution with the amount of 4 g/L, magnetic agitation 8 ~ 12 hours, is made CNTs is evenly spread in tin plating solution, and formula and the condition for preparing tin plating 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, Composite plating sample is made in 1100 and 1300 s.
(5) sample for obtaining composite plating be put into oxidation solution in, carry out anodized, anodic oxidation when Between be respectively 200,300 and 400 s, the formula of anodic oxidation solution is as follows:
(6) Sn/SnO/SnO is adulterated to the Ni-based CNTs of foam that step (5) obtains2The three-dimensional porous negative electrode material of stratiform is 60 It is dried in vacuo 8-12 hours in the environment of DEG C and obtains negative electrode material sample.
Fig. 3 is the Ni-based CNTs doping Sn/SnO/SnO of foam that 300 s are electroplated and aoxidize 200 s2The three-dimensional porous cathode of stratiform The SEM of material schemes, and is added after CNTs, has linear CNTs to be attached in foam nickel base, the oxide particle on surface becomes Porosity and looseness.
Fig. 4 is that nickel foam base carbon nanotube adulterates Sn/SnO/SnO2The XRD diagram of the three-dimensional porous negative electrode material of stratiform, from figure In obtained C, Ni, Sn, Sn4+、Sn2+Object mutually exist.
Obtained CNTs is adulterated into Sn/SnO/SnO2The three-dimensional porous negative electrode material assembling simulation button cell progressive of stratiform It can test.The negative electrode material for the different conditions that step (6) obtains is subjected to cut-parts with slitter, is with the negative electrode tab that cut-parts obtain Cathode, electrode, the button cell of assembling 2025 in argon atmosphere glove box, electrolyte are 1 mol/L to lithium metal as a comparison LiPF6, diaphragm is Celgard2400 type.Charge-discharge test is carried out in room temperature, and instrument is new prestige battery test system, test Voltage range is 0.01 ~ 3.0V, and test electric current is 0.1 C, obtains the electricity of the sample of different electroplating times and different oxidization times Chemical property, test result are as shown in table 1.
Table 1: different electroplating times and oxidization time sample chemical property contrast table
As can be seen from Table 1, the sample chemical property that different electroplating times and oxidization time obtain is different, electricity Time difference is plated, causes thickness of coating just different, electroplating time is too long, and thickness of coating is too thick, is easy to cause material in the circulating cycle It is not connected firmly and falls off with base, the chemical property of material is made to be deteriorated.
Embodiment 2
In conjunction with the embodiments 1, select 300 s oxidization time of electroplating time, 200 s to do laboratory sample, remaining step and embodiment 1 is identical.Using traditional lithium-ion battery test method, the first charge-discharge specific capacity for obtaining the cathode active principle is 1260 MAh/g, 50 circulations are later there are also 393.4 mAh/g, and average coulombic efficiency has reached 98%, and cycle performance is as shown in Figure 5.
Embodiment 3
In conjunction with the embodiments 1, select 300 s oxidization time of electroplating time, 250 s to do laboratory sample, remaining step and embodiment 1 is identical.Using traditional lithium-ion battery test method, the first charge-discharge specific capacity for obtaining the cathode active principle is 912 MAh/g, residual capacity is 288 mAh/g after 60 circulations, and average coulombic efficiency is 97% or so, and stable cycle performance is followed Ring performance is as shown in Figure 6.
Embodiment 4
In conjunction with the embodiments 1, select 700 s oxidization time of electroplating time, 200 s to do laboratory sample, remaining step and embodiment 1 is identical.Using traditional lithium-ion battery test method, the first charge-discharge specific capacity for obtaining the cathode active principle is 837 MAh/g, residual capacity is only less than 100 mAh/g after 50 circulations, but average coulombic efficiency stills remain in 97% left side The right side, cycle performance figure are as shown in Figure 7.
Comparative example 2,3 and 4, available difference electroplating time and oxidization time are different to the performance of material It influences, electroplating time is too long, causes active principle layer too thick, powder of detached is easy during cycle charge-discharge, to lead Material electrochemical performance is caused to be deteriorated, the suitable selection of time for being electroplated and aoxidizing has highly important influence to the performance of material.

Claims (7)

1. a kind of nickel foam base carbon nanotube adulterates Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform, including nickel foam is as collection Fluid, and it is attached to the carbon nano tube-doped Sn/SnO/SnO of the foam nickel surface2Layered porous three-dimensional structure；Using compound It is electroplated and anode oxidation method prepares the carbon nano tube-doped Sn/SnO/SnO2Layered porous three-dimensional structure；
Wherein, composite plating and anode oxidation method specific implementation are as follows: carbon nanotube is evenly spread in tin plating solution and is obtained Composite plating solution of tin；Nickel foam is put into the composite plating solution of tin prepared；Using compound electric plating method in foam nickel surface The tin metal coating of one layer of doped carbon nanometer pipe is electroplated, composite deposite carries out anodic oxidation.
2. nickel foam base carbon nanotube as described in claim 1 adulterates Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform, It is characterized in that, the outer diameter of the carbon nanotube is 10-100nm, and length is 0.5-10 μm.
3. nickel foam base carbon nanotube as described in claim 1 adulterates Sn/SnO/SnO2The three-dimensional porous negative electrode material of stratiform, It is characterized in that, the nickel foam is with a thickness of 0.5mm, porosity 95%.
4. a kind of nickel foam base carbon nanotube as described in any one of claims 1-3 adulterates Sn/SnO/SnO2Stratiform is three-dimensional porous The preparation method of negative electrode material, includes the following steps:
(1) first nickel foam is pre-processed, including surface degreasing and activation, then by treated carbon nanotube with 4-5g/L's Even concentration, which is distributed in tin plating solution, obtains composite plating solution of tin；
(2) tin of one layer of doped carbon nanometer pipe will be electroplated using compound electric plating method by pre-treatment step (1) resulting nickel foam The coat of metal；
(3) resulting composite deposite is electroplated in step (2) and carries out anodic oxidation, ultimately form carbon nano tube-doped Sn/SnO/SnO2 The oxide skin(coating) of stratiform three-dimensional structure；
(4) step (3) resulting material is dried in vacuo.
5. the preparation method according to claim 4, which is characterized in that the pretreated of nickel foam described in step (1) removes Oil, activation condition are specific as follows:
A) oil removing
What is used when configuration is except oil solution removes oil formula and except oil temperature are as follows: sodium hydroxide 30-40 g/L, sodium carbonate 20-50 g/ L, 20 ~ 30 g/L of sodium phosphate, 5 ~ 10 g/L of sodium metasilicate, 80 ~ 90 DEG C of temperature；
B) it activates
The activating recipe and activation temperature used when configuring activated solution are as follows: 25 ~ 75 g/L of sulfuric acid, temperature room temperature；More than Oil removing, activating recipe pre-processes nickel foam.
6. the preparation method according to claim 4, which is characterized in that the formula of the anodic oxidation solution of step (3) and anti- Answer condition as follows: 1 mol/L of oxalic acid, 1 ~ 10 min of oxidization time, 8 V of oxidation voltage, electroplating temperature room temperature, ultrasonic frequency 45 KHz；
The combination electrode that step (2) obtains is placed in the slot equipped with anodic oxidation solution, according to conditions above, carries out anodic oxygen Change.
7. the preparation method according to claim 4, which is characterized in that step (4) vacuum drying temperature is 60 DEG C, the time For 8-12h.
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