CN105529455B - A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof - Google Patents

A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof Download PDF

Info

Publication number
CN105529455B
CN105529455B CN201610049015.6A CN201610049015A CN105529455B CN 105529455 B CN105529455 B CN 105529455B CN 201610049015 A CN201610049015 A CN 201610049015A CN 105529455 B CN105529455 B CN 105529455B
Authority
CN
China
Prior art keywords
solution
ion battery
prism
lithium
anode material
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
CN201610049015.6A
Other languages
Chinese (zh)
Other versions
CN105529455A (en
Inventor
殷立雄
柴思敏
刘长青
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 CN201610049015.6A priority Critical patent/CN105529455B/en
Publication of CN105529455A publication Critical patent/CN105529455A/en
Application granted granted Critical
Publication of CN105529455B publication Critical patent/CN105529455B/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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Abstract

The present invention discloses a kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof, including：1) by SnCl4·5H2O and C6H12N4It 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, NaOH solution E is added dropwise into solution C, 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 prism and assembles spherical SnO2Anode material of lithium-ion battery.Preparation method of the present invention is at low cost, easy to operate, short preparation period；Prepared prism block assembles spherical SnO2Anode material of lithium-ion battery, prism block length are about 500nm, and diameter is about 30nm, and assembling ball size is about tens microns, and purity is high, crystallinity is strong, pattern is uniform, is applied to sodium-ion battery cathode, has higher capacity retention ratio.

Description

A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof
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 prisms to assemble spherical SnO2Anode material of lithium-ion battery and its preparation side The prism block of method, at low cost, easy to operate, short preparation period, acquisition assembles spherical SnO2Anode material of lithium-ion battery performance It is excellent.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of spherical SnO of prism assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O and C6H12N4It is dissolved in aliquots of deionized water respectively, is configured to solution A and solution B；Wherein, M in mass ratioSnCl4·5H2O：mC6H12N4=1:0.3~1:1.5；
2) B solution is slowly added to solution A under continuing magnetic force stirring action and forms homogeneous solution C, dropwise into solution C NaOH solution E is added, forms solution D；The volume of solution C and the volume ratio of solution E are 5:1~2:4；
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 it is spherical that freeze-drying obtains prism assembling SnO2Anode material of lithium-ion battery.
Further, in solution A Sn a concentration of 0.4~1.3mol/L.
Further, the solubility of NaOH solution E is 0.5~1.5mol/L.
Further, the condition of homogeneous hydro-thermal reaction is：At 120~240 DEG C, reaction time control exists for reaction temperature control 8~48h.
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 prism assembling2Prism assembling prepared by the preparation method of anode material of lithium-ion battery is spherical SnO2Anode 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 prism block assembles spherical SnO2Sodium Ion battery cathode material, prism block length are about 500nm, and diameter is about 30nm, and assembling ball size is about tens microns, purity Height, crystallinity is strong, pattern is uniform, is applied to sodium-ion battery cathode, and charge-discharge performance is excellent, in the electric current of 100mA/g Under density, discharge capacity can reach 408.768mAh/g for the first time, have higher capacity retention ratio after recycling 40 times.
Description of the drawings
Fig. 1 is that the prism prepared by example 1 of the present invention assembles spherical SnO2The SEM of anode material of lithium-ion battery schemes.
Fig. 2 is that the prism prepared by example 1 of the present invention assembles spherical SnO2Anode material of lithium-ion battery chemical property figure.
Specific implementation mode
Embodiment 1
A kind of spherical SnO of prism assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.4mol/L；In mass ratio mSnCl4·5H2O： mC6H12N4=1:0.3 by hexamethylenetetramine (C6H12N4) 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 0.5mol/L NaOH solution E are added, forms solution D, persistently stirs 0.5 afterwards；The volume of solution C and the volume ratio of solution E are 5:1；
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 120 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 prism assembling2Anode material of lithium-ion battery.
Fig. 1 is that the prism prepared by the embodiment of the present invention 1 assembles spherical SnO2The SEM of anode material of lithium-ion battery schemes. As can be seen from the figure the surface of sample is by prism block self assembly chondritic, and the length of prism block is about 500nm.Fig. 2 It is the spherical SnO of prism assembling prepared by the embodiment of the present invention 12Anode material of lithium-ion battery chemical property figure.From figure As can be seen that prepared prism assembles spherical SnO2Anode material of lithium-ion battery is under the current density of 100mA/g, for the first time Discharge capacity can reach 408.768mAh/g, have higher capacity retention ratio after recycling 40 times.
Embodiment 2
A kind of spherical SnO of prism assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 1.3mol/L；In mass ratio mSnCl4·5H2O： mC6H12N4=1:1.0 by hexamethylenetetramine (C6H12N4) 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 1.5mol/L NaOH solution E are added, forms solution D, persistently stirs 0.5 afterwards；The volume of solution C and the volume ratio of solution E are 3:2；
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 180 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 prism assembling2Anode material of lithium-ion battery.
Embodiment 3
A kind of spherical SnO of prism assembling2The preparation method of anode material of lithium-ion battery, includes the following steps：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.9mol/L；In mass ratio mSnCl4·5H2O： mC6H12N4=1:1.5 by hexamethylenetetramine (C6H12N4) 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 1.0mol/L NaOH solution E are added, forms solution D, persistently stirs 2 afterwards；The volume of solution C and the volume ratio of solution E are 2: 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 240 DEG C, the reaction time controls in 48h for degree control；
4) it waits for after reaction, taking out presoma, distinguishes centrifuge washing 2~3 times through deionized water and absolute ethyl alcohol, obtain Then white presoma is being dried in vacuo by prepared presoma in the subzero 60 DEG C of freezings 5h of freezing chamber of freeze drier 12h is dried at room temperature and obtains the spherical SnO of prism assembling in room2Anode material of lithium-ion battery.
SnO2Crystal has two kinds of tetragonal crystal system and rhombic system, and wherein orthorhombic phase is unstable, only in high temperature and pressure item The SnO for occurring under part, therefore synthesizing under normal conditions2Crystal belongs to the rutile-type of tetragonal crystal system, cell parameter a= 0.4738nm, c=0.3187nm.Recent studies indicate that SnO2Nano material photocatalysis, gas sensor, transistor, Li-Ion rechargeable battery and solar cell etc. all have stronger application prospect, it is considered to be most have the half of application prospect One of conductor nano material.SnO2The electrode material of base has big (the theoretical reversible capacity 781mAhg of embedding lithium capacity-1), cycle The advantages that performance is good, forthright good again, theoretical reversible capacity is high, and practical reversible capacity is also much larger than commercialization currently on the market The theoretical reversible capacity of various lithium battery carbon negative pole materials.
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.
The method of the present invention has the characteristics that manufacturing cost is low, easy to operate, short preparation period, prepared prism block group Fill spherical SnO2Anode material of lithium-ion battery, prism block length are about 500nm, and diameter is about 30nm, and assembling ball size is about Tens microns, purity is high, crystallinity is strong, pattern is uniform, is applied to sodium-ion battery cathode and is followed with excellent charge and discharge Ring performance.

Claims (2)

1. a kind of prism assembles spherical SnO2The preparation method of anode material of lithium-ion battery, which is characterized in that including following step Suddenly：
1) by SnCl4·5H2O is dissolved in deionized water, is configured to the solution A of a concentration of 0.4mol/L；In mass ratio mSnCl4·5H2O：mC6H12N4=1:0.3 hexamethylenetetramine 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 0.5mol/L NaOH solution E form solution D, rear lasting stirring；The volume of solution C and the volume ratio of solution E are 5:1；
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 120 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 prism and assembles spherical SnO2Anode material of lithium-ion battery；
Prism assembles spherical SnO2The surface of anode material of lithium-ion battery be by prism block self assembly chondritic, prism block Length is 500nm；Prepared prism assembles spherical SnO2Anode material of lithium-ion battery under the current density of 100mA/g, Discharge capacity reaches 408.768mAh/g for the first time.
2. a kind of prism described in claim 1 assembles spherical SnO2Prepared by the preparation method of anode material of lithium-ion battery Prism assembles spherical SnO2Anode material of lithium-ion battery.
CN201610049015.6A 2016-01-25 2016-01-25 A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof Active CN105529455B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610049015.6A CN105529455B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610049015.6A CN105529455B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof

Publications (2)

Publication Number Publication Date
CN105529455A CN105529455A (en) 2016-04-27
CN105529455B true CN105529455B (en) 2018-07-17

Family

ID=55771548

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610049015.6A Active CN105529455B (en) 2016-01-25 2016-01-25 A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105529455B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109167019A (en) * 2018-09-03 2019-01-08 大同新成新材料股份有限公司 A kind of cell negative electrode material and preparation method thereof and preparation facilities

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528808A (en) * 2014-12-27 2015-04-22 陕西科技大学 Preparation method of hollow tin dioxide microsphere
CN105036180A (en) * 2015-06-26 2015-11-11 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of tin oxide/zinc oxide nanometer flower-shaped composite material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939786B1 (en) * 2008-12-11 2011-03-25 Arkema France PROCESS FOR MANUFACTURING COMPOSITE SNO2 MATERIAL AND CARBON NANOTUBES AND / OR CARBON NANOFIBERS, MATERIAL OBTAINED BY THE PROCESS, ELECTRODE FOR LITHIUM BATTERY COMPRISING SAID MATERIAL.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104528808A (en) * 2014-12-27 2015-04-22 陕西科技大学 Preparation method of hollow tin dioxide microsphere
CN105036180A (en) * 2015-06-26 2015-11-11 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of tin oxide/zinc oxide nanometer flower-shaped composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"二氧化锡纳米材料的制备及其气敏性能研究";周晓明;《中国优秀硕士学位论文全文数据库》;20100915(第9期);第15-16页、第24页-第36页 *

Also Published As

Publication number Publication date
CN105529455A (en) 2016-04-27

Similar Documents

Publication Publication Date Title
CN107069020B (en) Preparation method of nickel-doped vanadium pentoxide nanosheet-shaped positive electrode material for lithium ion battery
CN105552351B (en) A kind of spherical SnO of nano particle assembling2Anode material of lithium-ion battery and preparation method thereof
CN105514392B (en) A kind of SnS2‑SnO2Nano-sheet sodium-ion battery anode material and preparation method thereof
CN107732180B (en) A kind of preparation method for water system sodium-ion battery anode composite material
CN105470455A (en) Modified lithium ion battery positive electrode material and preparation method therefor
CN105609766B (en) A kind of Ni doping SnS2Anode material of lithium-ion battery and preparation method thereof
CN108550829A (en) One kind having rose shape vanadium disulfide/carbon quantum dot composite material and preparation method and application
CN105449166B (en) A kind of preparation method of sodium-ion battery cathode pole piece
CN106299357A (en) There is bismuth sulfide electrode material and the application thereof of specific morphology structure
CN104078676A (en) Preparation method of sodium vanadyl phosphate/graphene composite material
CN108039486A (en) The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method
CN108054443A (en) Water system sodium ion secondary battery
CN109216684A (en) A kind of flower-shaped FeSxThe preparation method and purposes of/C nano composite material
CN106384674A (en) Aqueous rechargeable sodium-ion capacitor battery based on titanium phosphorus oxide cathode material
CN108807912A (en) A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C
CN103560280B (en) The chemical synthesizing method of lithium ion battery
CN105514404B (en) A kind of spherical SnO of nano particle assembling burr2Anode material of lithium-ion battery and preparation method thereof
CN105529455B (en) A kind of spherical SnO of prism assembling2Anode material of lithium-ion battery and preparation method thereof
CN107275580A (en) A kind of long circulation life height ratio capacity lithium sulfur battery anode material and lithium-sulphur cell positive electrode and its preparation
CN104766961B (en) Preparation method of low-specific-surface-area carbon/carbon composite negative electrode material of sodium ion battery
CN108075131A (en) One kind is based on NayNixMn1-xO2The water system energy-storage battery of structure richness sodium lamellar compound anode
CN106207110B (en) The preparation method and application of the hollow stannic oxide nanometer micro-sphere material of self-healing gel cladding
CN102070199A (en) Method for preparing micron frame-shaped manganese series lithium ion battery cathode material
CN105514405B (en) A kind of particle assembling cauliflower-shaped SnO2Anode material of lithium-ion battery and preparation method thereof
CN107039639A (en) A kind of preparation method of high power capacity sodium-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