CN105514404B - A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof - Google Patents

A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof Download PDF

Info

Publication number
CN105514404B
CN105514404B CN201610049012.2A CN201610049012A CN105514404B CN 105514404 B CN105514404 B CN 105514404B CN 201610049012 A CN201610049012 A CN 201610049012A CN 105514404 B CN105514404 B CN 105514404B
Authority
CN
China
Prior art keywords
solution
ion battery
nano particle
lithium
burr
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610049012.2A
Other languages
Chinese (zh)
Other versions
CN105514404A (en
Inventor
殷立雄
柴思敏
张�浩
马建中
黄剑锋
王菲菲
孔新刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201610049012.2A priority Critical patent/CN105514404B/en
Publication of CN105514404A publication Critical patent/CN105514404A/en
Application granted granted Critical
Publication of CN105514404B publication Critical patent/CN105514404B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention discloses a kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof, including：1) by SnCl4·5H2O and CO (NH2)2It is dissolved in aliquots of deionized water respectively, is configured to solution A and solution B；2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, N is added dropwise into solution CaOH solution Es form solution D；3) homogeneous hydro-thermal reaction is carried out；4) it waits for after reaction, taking out presoma, washing obtains white presoma, and freeze-drying obtains the spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery.Preparation method of the present invention is at low cost, easy to operate, short preparation period；The spherical SnO of prepared nano particle assembling burr2Anode material of lithium-ion battery charge-discharge performance is excellent, and under the current density of 50mA/g, discharge capacity can reach 1400mAh/g for the first time, has higher capacity and cyclical stability under high current density.

Description

A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and its system Preparation Method
Technical field
The present invention relates to sodium-ion battery technical field, more particularly to a kind of anode material of lithium-ion battery and its preparation side Method.
Background technology
Sodium-ion battery is a kind of model electrochemical power supply, has that raw material resources are abundant, cost is relatively low, specific capacity and effect The advantages that rate is higher more meets the requirement of scale stored energy application, is promoting extensive regenerative resource grid integration ability, is carrying There is application potential, simultaneously because its specific capacity height, light weight, long lifespan and nothing in terms of high electric energy service efficiency and power quality The significant advantages such as Memorability also have extensive in fields such as aerospace, hybrid-electric car and portable electronic devices Using.In this context, sodium-ion battery causes the extensive concern in worldwide, critical material and related skill in recent years Art progress is rapid.But for opposite lithium ion, sodium ion has larger ionic radius (0.102nm vs.0.076nm Of Li), this so that finding suitable embedding sodium material tool acquires a certain degree of difficulty.
Invention content
The purpose of the present invention is to provide a kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and Preparation method, manufacturing cost is low, easy to operate, short preparation period, and the particle of acquisition assembles spherical SnO2Sodium-ion battery Negative material is had excellent performance.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, including following step Suddenly：
1) by SnCl4·5H2O and CO (NH2)2It is dissolved in aliquots of deionized water respectively, is configured to solution A and solution B；Its In, m in mass ratioSnCl4·5H2O：mCO(NH2)2=1:0.4~1:1.5；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C N is addedaOH solution Es form solution D；The volume of solution C and the volume ratio of solution E are 5:2~3:4；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, carries out homogeneous hydro-thermal reaction；
4) it waits for after reaction, taking out presoma, washing obtains white presoma, and freeze-drying obtains nano particle assembling The spherical SnO of burr2Anode material of lithium-ion battery.
Further, in solution A Sn a concentration of 0.5~1.2mol/L.
Further, NaThe solubility of OH solution Es is 0.3~1.4mol/L.
Further, the condition of homogeneous hydro-thermal reaction is：At 80~220 DEG C, the reaction time controls 8 for reaction temperature control ~48h.
Further, the washing is specially to distinguish centrifuge washing 2~3 times through deionized water and absolute ethyl alcohol.
Further, the freeze-drying is specially that prepared presoma is subzero in the freezing chamber of freeze drier 50-60 DEG C of freezing 4-5h, then dries 10-12h at room temperature in vacuum drying cabinet.
A kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, prepared nanometer Particle assembles the spherical SnO of burr2Anode material of lithium-ion battery.
Compared with the existing technology, the invention has the advantages that：
Preparation method of the present invention is at low cost, easy to operate, short preparation period；Prepared nano particle assembling burr is spherical SnO2Anode material of lithium-ion battery particle size only has a few to tens of nanometers, and assembling ball size is about 300~400nm, purity Height, crystallinity is strong, pattern is uniform, is applied to sodium-ion battery cathode, and charge-discharge performance is excellent, close in the electric current of 50mA/g Under degree, discharge capacity can reach 1400mAh/g for the first time, have higher capacity and cyclical stability under high current density.
Description of the drawings
Fig. 1 is the spherical SnO of nano particle assembling burr prepared by example 1 of the present invention2The SEM of anode material of lithium-ion battery Figure.
Fig. 2 is the spherical SnO of nano particle assembling burr prepared by example 1 of the present invention2Anode material of lithium-ion battery electrification Learn performance map.
Specific implementation mode
Embodiment 1
A kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, including following step Suddenly：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.5mol/L；In mass ratio mSnCl4·5H2O： mCO(NH2)2=1:0.4 by urea (CO (NH2)2) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 0.3mol/L N are addedaOH solution Es form solution D, persistently stir 0.5h afterwards；The volume of solution C and the volume ratio of solution E are 5:2；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 80 DEG C, the reaction time controls in 8h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 2 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, subzero 50 DEG C of the freezing chamber by prepared presoma in freeze drier freezes 5h, then in vacuum drying cabinet 10h is dried at room temperature obtains the spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery.
Fig. 1 is the spherical SnO of nano particle assembling burr prepared by the embodiment of the present invention 12Anode material of lithium-ion battery SEM figure.As can be seen from the figure the surface of sample is that the burr that is assembled by nano particle is spherical, and nanoparticle size is about It it is several nanometers, the grain size for assembling acanthosphere is about 150~180nm.Fig. 2 is the nano particle assembling prepared by the embodiment of the present invention 1 The spherical SnO of burr2Anode material of lithium-ion battery chemical property figure.As can be seen from the figure prepared nano particle assembles hair Acanthosphere shape SnO2Anode material of lithium-ion battery, under the current density of 50mA/g, discharge capacity can reach for the first time 1400mAh/g has higher capacity and cyclical stability under high current density.
Embodiment 2
A kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, including following step Suddenly：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.8mol/L；In mass ratio mSnCl4·5H2O： mCO(NH2)2=1:0.9 by urea (CO (NH2)2) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 0.8mol/L N are addedaOH solution Es form solution D, persistently stir 1h afterwards；The volume of solution C and the volume ratio of solution E are 4: 3；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 150 DEG C, the reaction time controls in 36h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, subzero 60 DEG C of the freezing chamber by prepared presoma in freeze drier freezes 4h, then in vacuum drying cabinet 11h is dried at room temperature obtains the spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery.
Embodiment 3
A kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, including following step Suddenly：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 1.2mol/L；In mass ratio mSnCl4·5H2O： mCO(NH2)2=1:1.5 by urea (CO (NH2)2) be added in aliquots of deionized water, it is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C 1.4mol/L N are addedaOH solution Es form solution D, persistently stir 2h afterwards；The volume of solution C and the volume ratio of solution E are 3: 4；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature At 220 DEG C, the reaction time controls in 48h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 3 times through deionized water and absolute ethyl alcohol, obtain white Color presoma, subzero 50 DEG C of the freezing chamber by prepared presoma in freeze drier freezes 4h, then in vacuum drying cabinet 12h is dried at room temperature obtains the spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery.
Stannic oxide also known as tin oxide, chemical formula SnO2, belong to group IV-VI Binary compound semiconductor, powder presents white Color or yellow, 1127 DEG C of molten point, boiling point are higher than 190 DEG C, theoretical density 6.95g/cm3, belong to amphoteric oxide, dissolve in Strong acid and highly basic.Cell parameter a=0.4738nm, b=0.4738mn, c=3.187nm, O2-Ionic radius 0.14nm, Sn4+From Sub- radius 0.072nm, interior each structure cell includes two SnO2Molecule.Recent studies indicate that SnO2Nano material photocatalysis, Gas sensor, transistor, Li-Ion rechargeable battery and solar cell etc. all have stronger application prospect, are considered It is one of the semiconductor nano material for most having application prospect.SnO2The electrode material of base has big (the theoretical reversible appearance of embedding lithium capacity Measure 781mAhg-1), good cycle, it is forthright good again the advantages that, theoretical reversible capacity is high, and practical reversible capacity is also remote More than the theoretical reversible capacity of various lithium battery carbon negative pole materials commercial currently on the market.
Since granule-morphology may also can affect to the chemical property of sample, particle is smaller, specific surface Product is bigger, then contact of the material with electrolyte is better, Na+Migration distance can also shorten, be more advantageous to sodium-ion battery in this way The promotion of negative material high rate performance.

Claims (2)

1. a kind of spherical SnO of nano particle assembling burr2The preparation method of anode material of lithium-ion battery, which is characterized in that including Following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.5mol/L；In mass ratio mSnCl4·5H2O：mCO(NH2)2=1:0.4 urea is added in aliquots of deionized water, is configured to solution B；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, be added dropwise into solution C 0.3mol/L NaOH solution Es form solution D, persistently stir 0.5h afterwards；The volume of solution C and the volume ratio of solution E are 5:2；
3) it waits for after reaction, solution D being put into hydrothermal reaction kettle and is sealed, is put into homogeneous hydro-thermal reaction instrument, reaction temperature control At 80 DEG C, the reaction time controls in 8h system；
4) it waits for after reaction, taking out presoma, centrifuge washing is distinguished 2 times through deionized water and absolute ethyl alcohol, before obtaining white Body is driven, subzero 50 DEG C of the freezing chamber by prepared presoma in freeze drier freezes 5h, then in vacuum drying cabinet room temperature Lower dry 10h obtains the spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery；
The prepared spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery is the burr ball assembled by nano particle Shape, the grain size for assembling acanthosphere are 150~180nm；The spherical SnO of prepared nano particle assembling burr2Sodium-ion battery cathode material Material, under the current density of 50mA/g, discharge capacity can reach 1400mAh/g for the first time.
2. a kind of spherical SnO of nano particle assembling burr described in claim 12The preparation method of anode material of lithium-ion battery, The prepared spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery.
CN201610049012.2A 2016-01-25 2016-01-25 A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof Active CN105514404B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610049012.2A CN105514404B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610049012.2A CN105514404B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105514404A CN105514404A (en) 2016-04-20
CN105514404B true CN105514404B (en) 2018-08-24

Family

ID=55722215

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610049012.2A Active CN105514404B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105514404B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807907B (en) * 2018-06-12 2021-06-08 陕西科技大学 Method for preparing particle self-assembly spherical tin monoxide/tin dioxide sodium ion battery cathode material by one-step method
CN108832094B (en) * 2018-06-12 2021-05-04 陕西科技大学 Method for preparing spherical tin sulfide/stannous sulfide lithium ion battery cathode material by one-step method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101263287B1 (en) * 2006-12-01 2013-05-10 삼성코닝정밀소재 주식회사 Method of manufacturing tin oxide powder
CN103864139A (en) * 2014-02-18 2014-06-18 上海大学 Preparation method of three-dimensional layered multilevel flower-shaped stannic oxide microsphere
CN104528808A (en) * 2014-12-27 2015-04-22 陕西科技大学 Preparation method of hollow tin dioxide microsphere
CN104876259A (en) * 2015-05-07 2015-09-02 浙江大学 Preparation method of open tin dioxide hollow spheres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101263287B1 (en) * 2006-12-01 2013-05-10 삼성코닝정밀소재 주식회사 Method of manufacturing tin oxide powder
CN103864139A (en) * 2014-02-18 2014-06-18 上海大学 Preparation method of three-dimensional layered multilevel flower-shaped stannic oxide microsphere
CN104528808A (en) * 2014-12-27 2015-04-22 陕西科技大学 Preparation method of hollow tin dioxide microsphere
CN104876259A (en) * 2015-05-07 2015-09-02 浙江大学 Preparation method of open tin dioxide hollow spheres

Also Published As

Publication number Publication date
CN105514404A (en) 2016-04-20

Similar Documents

Publication Publication Date Title
CN105742602B (en) A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof
CN105552351B (en) A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof
CN105355880B (en) A kind of LiFePO4/ C is modified the preparation method of tertiary cathode material
CN105514392B (en) A kind of SnS2‑SnO2Nano-sheet sodium-ion battery anode material and preparation method thereof
CN103928672B (en) A kind of positive electrode active material for lithium ion battery and preparation method thereof
CN104134783B (en) Nano nickel sulphide/grapheme composite positive electrode material and preparation method thereof
CN103972497B (en) Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof
CN106876682B (en) A kind of manganese oxide with porous structure/nickel micron ball and its preparation and application
CN107732180B (en) A kind of preparation method for water system sodium-ion battery anode composite material
CN101609884B (en) Method for preparing negative pole material SnS2 of lithium ion battery
CN105609766B (en) A kind of Ni doping SnS2Anode material of lithium-ion battery and preparation method thereof
CN105098181A (en) Preparation method for nano-flake SnS2 sodium-ion battery negative electrode material with good rate capability
CN106450204B (en) A kind of high circulation performance SnS2/TiO2The preparation method of anode material of lithium-ion battery
CN102795666A (en) Method for preparing vanadium pentoxide cathode nano-material of lithium-ion battery
CN104993116B (en) A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method
CN104078676A (en) Preparation method of sodium vanadyl phosphate/graphene composite material
CN108054443A (en) Water system sodium ion secondary battery
CN108039486A (en) The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method
CN108878864A (en) A kind of spherical shape sodium-ion battery positive material and preparation method thereof
CN106299357A (en) There is bismuth sulfide electrode material and the application thereof of specific morphology structure
CN105481004B (en) A kind of high electric property tin dioxide nanometer tube and preparation method thereof
CN106384674A (en) Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material
CN103441239A (en) Synthetic method for nanoscale ternary cathode material
CN105514404B (en) A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof
CN106564934B (en) A kind of particle assembles spherical SnS2The preparation method of anode material of lithium-ion battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant