CN105552320B - A kind of Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof - Google Patents

A kind of Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof Download PDF

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Publication number
CN105552320B
CN105552320B CN201510915320.4A CN201510915320A CN105552320B CN 105552320 B CN105552320 B CN 105552320B CN 201510915320 A CN201510915320 A CN 201510915320A CN 105552320 B CN105552320 B CN 105552320B
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stratiform
foam
dimensional porous
negative electrode
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CN105552320A (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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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
    • H01M4/36—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
    • 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
    • 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
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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 Sn/SnO/SnO2Three-dimensional porous negative electrode material of stratiform and preparation method thereof, including nickel foam is as collector, and is attached to the Sn/SnO/SnO of the foam nickel surface2Stratiform three-dimensional porous structure.The present invention first carries out surface preparation to the nickel foam with three-dimensional structure, then by treated, foam nickel base is put into tin plating solution, is electroplated, then carries out anodized to resulting material, by vacuum drying, a kind of Ni-based Sn/SnO/SnO of foam has finally been prepared2The negative electrode material of stratiform three-dimensional porous structure.The three-dimensional porous lithium ion battery negative material of stratiform of the present invention has excellent chemical property, and first discharge specific capacity reaches 837mAh/g, and average coulombic efficiency maintains 95% or so after 40 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 Ni-based Sn/SnO/SnO of foam2The three-dimensional porous negative electrode material of stratiform and its preparation Method
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 Ni-based Sn/SnO/SnO of foam2Three-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.Such as Wang [Y. Wang et al. 21 (2009) 3210-3215 of Chemistry of Materials.] using CNTs as template, by chemical vapour deposition technique system For the tin base cathode material wrapped up by CNTs has been gone out, which shows good chemical property, in 80 times fill of process After discharge cycles, specific capacity still has 526mAh/g, but batch production is had any problem.[the H. Uchiyama et such as Uchiyama Al. Electrochem Commun. 10 (2008) 52-55] it is prepared for the oxidation of reticular structure in aqueous solution with hydro-thermal method Tin nano crystal, the tin negative pole material prepared with this method, first charge-discharge capacity have reached 900mAh/g.Du etc. [55 (2010) 2527-2541 of Z. J. Du et al. Electrochimica Acta.] uses the method for chemical plating by tin It is attached on the foam copper with three-D space structure, first discharge specific capacity is 737 mAh/g, after 20 circulations also 97% capacity is remaining, achieves 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.Current many researchers go to prepare lithium ion battery negative with electro-plating method Pole material, and make great progress, [the W. H. Pu et al. Electrochimia Acta. 50 (2005) such as Pu 4140-4145] with electric plating method tin film is electroplated in copper foil surface, in conjunction with heat treatment process, it is negative to be prepared for Sn-Cu alloy Pole material, average coulombic efficiency reach 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, Al, Cu etc.), and three-dimensional foam metal has than table The features such as area is big, porous can alleviate the enormousness strain that lithium ion battery material generates in charge and discharge process, from And the cycle performance of reinforcing material.Material in plating can obtain different structures, and the material of more layer structures can not only increase The binding force of strong coating and substrate, keeps coating not easy to fall off in charge and discharge process, improves the cycle performance of material, more can Outstanding capacity is provided.[the X. L. Chen et al. Journal of Power Sources. 211 such as Chen (2012) 129-132] tin is electroplated in the tobacco mosaic virus (TMV) (tobacco mosaic virus) with three-D space structure On, this 3D negative electrode material presents good circulation ability, also there is the residual capacity of 560 mAh/g after 100 circulations, times Rate performance is also very excellent.[the N. Tamura et al. Journal of Power Sources. 107 such as Tamura (2002) 48-55] in order to enhance the binding force of tin coating Yu copper foil substrate, heat treatment process is combined after plating, in tin layers and copper Tin-copper composite layer is generated between foil substrate, and the comparison not being heat-treated, residual capacity increases from 20% after 10 circulations To 94%, the materials'use service life is improved.
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 Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof.It proposes It uses three-dimensional porous material nickel foam as collector, Sn/SnO/SnO is prepared using plating and anode oxidation method2Stratiform is three-dimensional The negative electrode material of porous structure, nickel foam porosity is big, can alleviate tin material huge volume change in charge and discharge process, The structure of multilevel oxide improves the capacity of material.The Ni-based Sn/SnO/SnO of foam2The three-dimensional porous negative electrode material of stratiform is special Structure, specific capacity height, stable cycle performance, and be suitable for industrialized production.
To achieve the goals above, technical scheme is as follows:
The Ni-based Sn/SnO/SnO of a kind of foam of the invention2The three-dimensional porous negative electrode material of stratiform, including nickel foam is as collection Fluid, and it is attached to the Sn/SnO/SnO of the foam nickel surface2Stratiform three-dimensional porous structure.
Preferably, the nickel foam is with a thickness of 0.5 mm, porosity 95%.
Preferably, the Sn/SnO/SnO2Stratiform three-dimensional porous structure is prepared using anodizing.
Preferably, the Sn/SnO/SnO2The preparation of stratiform three-dimensional porous structure implements are as follows: nickel foam is electroplated one Layer tin metal coating, then coating is subjected to anodic oxidation.
Preferably, the preparation method of the material includes the following steps:
(1) nickel foam is pre-processed, including surface degreasing and activation；
(2) one layer of tin metal coating will be electroplated by step (1) pretreated nickel foam；
(3) resulting coating is electroplated in step (2) and carries out anodic oxidation, ultimately form Sn/SnO/SnO2Stratiform is three-dimensional more The oxide skin(coating) of pore structure；
(4) step (3) resulting material is dried in vacuo.
A kind of above-mentioned Ni-based Sn/SnO/SnO of foam of the invention2The preparation method of the three-dimensional porous negative electrode material of stratiform, packet Include following steps:
(1) nickel foam is pre-processed, including surface degreasing and activation；
(2) one layer of tin metal coating will be electroplated by step (1) pretreated nickel foam；
(3) resulting coating is electroplated in step (2) and carries out anodic oxidation, ultimately form Sn/SnO/SnO2Stratiform is three-dimensional more The oxide skin(coating) of pore 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.
Preferably, the solution of electrotinning formula of step (2) is as follows
Nickel foam is placed on electroplating device, is put into the solution of electrotinning, is electroplated according to conditions above, tin metal plating is obtained Layer.
Preferably, the formula of the anodic oxidation solution of step (3) and reaction condition are as follows:
The electrode that step (2) obtains is placed in the slot equipped with anodic oxidation solution, according to conditions above, carries out anodic oxygen Change.The anodic oxidation refers to using metal or metal alloy as anode in suitable electrolyte, by anode current, Make the method that anode surface is aoxidized.Anodic oxidation principle is simple, and technique requires low, suitable industrialized production.
Preferably, step (4) vacuum drying temperature is 60 DEG C, and the time is 8 ~ 12 h.
The beneficial effects of the present invention are:
The present invention selects nickel foam as collector, can greatly increase the specific surface area of electrode, and is active material Certain buffer function is played in the great change of charge and discharge process volume, can improve lithium ion insertion and deintercalation to a certain extent Efficiency, to improve the chemical property of electrode.
The method that the present invention uses anodic oxidation, can obtain Sn/SnO/SnO2Stratiform three-dimensional porous structure, is capable of providing More capacity, and more stable chemical property can alleviate electrode material in conjunction with the three-D space structure of nickel foam Bulk strain in charge and discharge process makes material have more preferably stability.
The Ni-based Sn/SnO/SnO of foam of the present invention2The three-dimensional porous negative electrode material structure of stratiform is special, has charge and discharge specific volume The advantages of amount is high, stable cycle performance, and be suitable for industrialized production.The Ni-based Sn/SnO/SnO of foam of the present invention2Stratiform is three-dimensional more Hole negative electrode material first charge-discharge specific capacity is 837 mAh/g, while also having excellent cycle performance and coulomb outstanding Efficiency, for 40 circulations later there are also 306 mAh/g, average coulombic efficiency is maintained at 95% or so.This is because following two points factor The result of generation: 1, nickel foam is as collector, because being porous three-dimensional material, high porosity and big specific surface Product can largely alleviate lithium ion insertion and change with enormousness caused by deintercalation, promote the stability of material.2, Using the method for anodic oxidation, it is prepared with Sn/SnO/SnO2Stratiform three-dimensional porous structure negative electrode material, can not only mention High charge-discharge specific capacity, moreover it is possible to reduce volume change.
The Ni-based Sn/SnO/SnO of foam of the present invention2The preparation method of the three-dimensional porous negative electrode material of stratiform has following prominent Advantage: 1, anodizing preparation has Sn/SnO/SnO2The negative electrode material of stratiform three-dimensional porous structure, method is simple, practical Property is strong, and production cost is low；2, practical non-cyanide solution is electroplating solution, and no pollution to the environment meets environmental requirement；3, it produces Cost is relatively low, and preparation process is simple and easy.
A kind of Ni-based Sn/SnO/SnO of foam of the present invention2The surface topography of the three-dimensional porous negative electrode material of stratiform is to pass through scanning (FE-SEM, S-4800, Hitachi, the Japan) of determination of electron microscopy.
A kind of Ni-based Sn/SnO/SnO of foam of the present invention2The object of the three-dimensional porous negative electrode material of stratiform is mutually to pass through XRD method Measurement.
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 the Ni-based Sn/SnO/SnO of foam of the present invention2The preparation flow schematic diagram of the three-dimensional porous negative electrode material of stratiform；
Fig. 2 is to scheme in embodiment 1 without the SEM of the nickel foam metal of any processing；
Fig. 3 is the Ni-based Sn/SnO/SnO of foam of 300 s oxidization time of electroplating time, 200 s2The three-dimensional porous cathode of stratiform The SEM of material schemes；
Fig. 4 is the Ni-based Sn/SnO/SnO of foam of 300 s oxidization time of electroplating time, 200 s2The three-dimensional porous cathode of stratiform The amplification SEM of material schemes；
Fig. 5 is the Ni-based Sn/SnO/SnO of foam of 300 s oxidization time of electroplating time, 200 s2The three-dimensional porous cathode of stratiform The X-ray diffractogram of material；
Fig. 6 is the 300 Ni-based Sn/SnO/SnO of s oxidization time 200s foam of electroplating time2The three-dimensional porous negative electrode material of stratiform Cycle performance figure.
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 the design cycle schematic diagram entirely tested, and Fig. 2 is without any The SEM of the nickel foam metal of processing schemes.
(1) nickel foam pre-processes
Oil removal treatment, solution allocation are as follows:
It is activated again, solution allocation is as follows
(2) the solution of electrotinning and anodic oxidation solution are prepared
Formula and the condition for preparing the solution of electrotinning are as follows:
(3) nickel foam is put into the tin plating solution prepared, electroplating time be respectively 300s, 500s, 700s, 900s, Electrotinning sample is made in 1000s, 1300s.
(4) sample that step (3) plating obtains is put into oxidation solution, carries out anodized, anodic oxidation Time be respectively 200s, 300s, 400 s, the formula of anodic oxidation solution is as follows:
(5) the Ni-based Sn/SnO/SnO of foam that step (4) is obtained2Ring of the three-dimensional porous negative electrode material of stratiform at 60 DEG C It is dried in vacuo 8 ~ 12 hours under border and obtains negative electrode material sample.
Fig. 3, Fig. 4 are the Ni-based Sn/SnO/SnO of foam that 300 s are electroplated and aoxidize 200 s2The three-dimensional porous negative electrode material of stratiform SEM figure, can be seen that rhombohedra particle is uniformly adhered on netted foam nickel skeleton in conjunction with two pictures.
Fig. 5 is the Ni-based Sn/SnO/SnO of foam2The XRD diagram of the three-dimensional porous negative electrode material of stratiform, Cong Tuzhong obtained Ni, Sn、Sn4+、Sn2+Object mutually exist.
Table 1: different electroplating times and oxidization time sample chemical property contrast table
The Sn/SnO/SnO that will be obtained2The three-dimensional porous negative electrode material assembling simulation button cell of stratiform is tested for the property. The negative electrode material for the different conditions that step (5) obtains is subjected to cut-parts with slitter, is cathode with the negative electrode tab that cut-parts obtain, gold Belong to lithium electrode as a comparison, 2025 button cell is assembled in argon atmosphere glove box, electrolyte is the LiPF of 1 mol/L6, Diaphragm is Celgard2400 type.Charge-discharge test is carried out in room temperature, and instrument is new prestige battery test system, test voltage range For 0.01 ~ 3.0V, test electric current is 0.1 C, obtains the chemical property of the sample of different electroplating times and different oxidization times, Its test result is as shown in table 1.
As can be seen from Table 1, the sample chemical property that different electroplating times and oxidization time obtain be it is different, Electroplating time is different, causes thickness of coating just different, electroplating time is too long, and thickness of coating is too thick, and material is easy to cause to recycle In be not connected firmly and fall off with base, so that the chemical property of material is deteriorated.
Embodiment 2
In conjunction with the embodiments 1, select 300 s oxidization time 200s of electroplating time to do laboratory sample, remaining step and embodiment 1 It 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, 40 circulations are later there are also 306 mAh/g, and average coulombic efficiency has reached 95%, and cycle performance figure is as shown in Figure 6.

Claims (6)

1. a kind of Ni-based Sn/SnO/SnO of foam2The three-dimensional porous negative electrode material of stratiform, including nickel foam is as collector, and attachment In the Sn/SnO/SnO of the foam nickel surface2Stratiform three-dimensional porous structure；
The Ni-based Sn/SnO/SnO of the foam2The preparation method of the three-dimensional porous negative electrode material of stratiform, includes the following steps:
(1) nickel foam is pre-processed, including surface degreasing and activation；
(2) one layer of tin metal coating will be electroplated by step (1) pretreated nickel foam；
(3) resulting coating is electroplated in step (2) and carries out anodic oxidation, ultimately form Sn/SnO/SnO2Stratiform three-dimensional porous structure Oxide skin(coating)；
(4) step (3) resulting material is dried in vacuo；
The formula and reaction condition of the anodic oxidation solution of step (3) are as follows:
Oxalic acid 1mol/L Oxidization time 1~10min Oxidation voltage 8V Electroplating temperature Room temperature Ultrasonic frequency 45KHz
The electrode that step (2) obtains is placed in the slot equipped with anodic oxidation solution, according to conditions above, carries out anodic oxidation.
2. negative electrode material as described in claim 1, which is characterized in that the nickel foam is with a thickness of 0.5mm, porosity 95%.
3. a kind of Ni-based Sn/SnO/SnO of foam as claimed in claim 1 or 22The preparation side of the three-dimensional porous negative electrode material of stratiform Method, which comprises the steps of:
(1) nickel foam is pre-processed, including surface degreasing and activation；
(2) one layer of tin metal coating will be electroplated by step (1) pretreated nickel foam；
(3) resulting coating is electroplated in step (2) and carries out anodic oxidation, ultimately form Sn/SnO/SnO2Stratiform three-dimensional porous structure Oxide skin(coating)；
(4) step (3) resulting material is dried in vacuo；
The formula and reaction condition of the anodic oxidation solution of step (3) are as follows:
The electrode that step (2) obtains is placed in the slot equipped with anodic oxidation solution, according to conditions above, carries out anodic oxidation.
4. preparation method according to claim 3, 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 30~40g/L Sodium carbonate 20~50g/L Sodium phosphate 20~30g/L Sodium metasilicate 5~10g/L Temperature 80~90 DEG C
B) it activates
The activating recipe and activation temperature used when configuring activated solution are as follows:
Sulfuric acid 25~75g/L Temperature Room temperature
Oil removing, activating recipe more than pre-process nickel foam.
5. preparation method according to claim 3, which is characterized in that the solution of electrotinning formula of step (2) is as follows
Stannous sulfate 30g/L Sulfuric acid 110mL/L SR-1 open cylinder agent 40mL/L Temperature 20~40 DEG C Cathode-current density 1~1.5A/dm2 Electroplating in ultrasonic field frequency 45KHz Electroplating time 2~25min
Nickel foam is placed on electroplating device, is put into the solution of electrotinning, is electroplated according to conditions above, tin metal coating is obtained.
6. preparation method according to claim 3, which is characterized in that step (4) vacuum drying temperature is 60 DEG C, the time For 8-12h.
CN201510915320.4A 2015-12-11 2015-12-11 A kind of Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof Expired - Fee Related CN105552320B (en)

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CN110706941B (en) * 2019-10-18 2020-11-24 中国地质大学（北京） Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material
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