CN105762349B - More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application - Google Patents

More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application Download PDF

Info

Publication number
CN105762349B
CN105762349B CN201610066853.4A CN201610066853A CN105762349B CN 105762349 B CN105762349 B CN 105762349B CN 201610066853 A CN201610066853 A CN 201610066853A CN 105762349 B CN105762349 B CN 105762349B
Authority
CN
China
Prior art keywords
preparation
shell
metal oxide
ball
hydro
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
CN201610066853.4A
Other languages
Chinese (zh)
Other versions
CN105762349A (en
Inventor
王丹
王江艳
毛丹
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.)
Zhongke Huisheng (Beijing) Pharmaceutical Technology Co.,Ltd.
Original Assignee
Institute of Process Engineering of CAS
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 Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201610066853.4A priority Critical patent/CN105762349B/en
Publication of CN105762349A publication Critical patent/CN105762349A/en
Application granted granted Critical
Publication of CN105762349B publication Critical patent/CN105762349B/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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 present invention relates to more shell-layer metal oxide hollow balls synthesized based on Anion-adsorption and its preparation method and application.The present invention is by the use of carbon ball prepared by hydro-thermal method as template, and by the way that carbon ball template is dispersed in anionic metal salting liquid, and further high-temperature roasting obtains the metallic oxide hollow sphere with more shell structurres；The hollow ball prepared using this method, its shell number can between two to five layers modulation, size and shell thickness are controllable, the efficient set advantage of low-dimension nano material and three-dimensional hollow structure, applied to field of lithium ion battery, the performance for being superior to nanometer sheet or single shell hollow sphere is shown, is had broad application prospects.

Description

More shell-layer metal oxide hollow balls and its preparation side based on Anion-adsorption synthesis Method and purposes
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of more shell-layer metal oxide hollow balls and its preparation Method and purposes more particularly to a kind of more shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and preparation method thereof And purposes.
Background technology
At present, more shell hollow micron/nanostructureds have large specific surface area, load capacity are high, density is light, internal cavities with And the features such as by the shell wall of low-dimensional nano particle or nanometer bar construction, thus all realize and be widely used in many fields, than Such as medicament slow release, catalysis, sensing, water pollution control, nano-reactor and energy-storage system.Wherein, more shell metallic oxidations Object hollow ball is used as lithium ion battery electrode material, and not only electrode material and electrolyte contacts area are big, lithium ion storage site More, so as to improve specific capacity height, and internal cavities can be followed with buffer volumes expansion and structural tension and stress so as to improve Ring stability.In addition, lithium ion and electron-transport are apart from short, reactivity height, so as to which the high current for improving lithium ion battery is put Electric energy power.
At present, the preparation method of more shell oxide hollow spheres mainly has two kinds of soft template method and hard template method.For soft Template reports in existing document prepare Cu using surfactant cetyl trimethylammonium bromide at present2The more shells of O are empty Bulbus cordis (Angewandte Chemie-International Edition, 2007,46:1489-1492) or using FC4 and The vesica that F127 resins are self-assembly of prepares SiO for soft template2More shell hollow sphere (Journal Material Chemistry,2010,20:4595-4601).But these soft template methods are generally only applicable to the spy that above-mentioned document is related to Determine the preparation of the more shell hollow spheres of compound, it is difficult to be applied to the preparation of the more shell hollow spheres of other oxides.
Hard template method generally use polystyrene (PS) ball, silica spheres or carbon ball etc. are used as template.Have at present Document report carries out sulfonation using the concentrated sulfuric acid using PS balls as template to PS ball surfaces, modifies one layer of SO3-H+Ion, then inhale Attached Ti presomas, and obtained TiO through high-temperature calcination2Double shell hollow sphere (Angewandte Chemie-International Edition,2005,44,6727-6730).However this synthetic method complex procedures, preparation flow are long, and obtain hollow The shell number of ball is limited (being no more than 3 layers).
It is template to also have document report to utilize electronegative carbon ball at present, cationic by electrostatic interaction adsorbing metal, Finally by one-step calcination method remove carbon ball template, you can obtain more shell hollow spheres (X.Y.Lai, J.Li, B.A.Korgel, Z.H.Dong,Z.M.Li,F.B.Su,J.Du,D.Wang.Angew.Chem.Int.Ed.,2011,50:2738-2741)； CN102464304A also discloses the more shell-layer metal oxide hollow balls being prepared using the above method； CN103247777A also discloses that, using metal cation, specially cobaltosic oxide is adsorbed to make with electronegative carbon ball The more shell hollow sphere negative materials of standby cobaltosic oxide.However, since many metal ion presomas are usually with anionic form (such as VO3-、MnO4 2-、MoO4 2-、CrO4 2-、W7O24 6-Deng) existing, although can exist at low ph values with cationic form, But carbon ball template institute is negatively charged to be reduced rapidly as pH value reduces, so as to cause metal cation adsorbance very It is limited, it is difficult to synthesize the metal oxide hollow structure with more shells.
Therefore, how a kind of specific surface area with extensive universality and with bigger is provided, electrode material and electricity can be made Solution liquid contact is more preferable, lithium ion storage site is more, and improving more shell-layer metal oxide hollow-core constructions of specific capacity has become mesh Preceding urgent problem to be solved.
Invention content
For the deficiency of the more shell-layer metal oxide hollow balls of prior art preparation, the purpose of the present invention is to provide one kind Easy to operate, controllability is strong, and pollution is small and has the preparation method of more shell-layer metal oxide hollow balls of extensive universality.
For this purpose, present invention employs following technical schemes：
In a first aspect, the present invention provides a kind of more shell-layer metal oxide hollow balls based on Anion-adsorption synthesis Preparation method, the method includes：By the use of carbon ball prepared by hydro-thermal method as template, the carbon ball template is scattered in metal the moon It is fired to obtain more shell-layer metal oxide hollow balls in ion salt solution.
Heretofore described " more shell-layer metal oxide hollow balls " refers to that shell number is at least two layers, shell wall is by metal oxygen Compound nano particle and/or nanometer rods accumulation form and internal cavities are at least one spherical structure, typical but unrestricted Property example be there is metallic oxide hollow sphere that shell number is 2 layers, 3 layers, 4 layers or 5 layers or at least two layers of shell The V of layer2O5Hollow ball, MnO2Hollow ball, WO3Hollow ball, MoO3Hollow ball or Cr2O3Hollow ball etc..
The preparation method of heretofore described more shell-layer metal oxide hollow balls is a kind of based on Anion-adsorption synthesis The method of more shell-layer metal oxide hollow balls.It is to provide the moon by anionic metal salting liquid in the preparation method The metal oxide precursor of ionic species；It can not only increase it using the metal ion presoma of the anionic form closing Into adsorbance in the process, enable the anionic metal deeper into carbon ball inside, and metal oxide sky can be increased The number of plies of bulbus cordis makes it have the specific surface area of bigger, more so as to when applied to anode material for lithium-ion batteries, have Lithium ion storage site greatly improves the specific capacitance of lithium ion battery.
In the preparation method, the anionic form metal ion presoma used usually has higher valence state so that The metal oxide being prepared also has higher valence state, is able to preferably control the valence state of product.For example, by using relatively low The Mn of valence state2+Cation is presoma, and the Mn compared with lower valency can only be prepared2O3；And by using with higher valence state MnO4 2-Anion is presoma, and the MnO of higher valence state can be prepared2。
Heretofore described anionic metal salt can be in vanadate, manganate, molybdate, chromate or tungstates Any one or at least two mixture, mixture of the typical but non-limiting mixing example for vanadate and manganate, The mixture of molybdate and chromate, the mixture of manganate, molybdate and chromate, vanadate, manganate, molybdate, chromium The mixture of hydrochlorate and tungstates.
Illustratively, the anionic metal salt is preferably NH4VO3、K2MnO4、(NH4)2MoO4、(NH4)2CrO4Or (NH4)6W7O24·6H2In O any one or at least two mixture, it is typical but non-limiting mixing example be NH4VO3 And K2MnO4Mixture, K2MnO4(NH4)2MoO4Mixture, (NH4)2MoO4、(NH4)2CrO4(NH4)6W7O24· 6H2The mixture of O.
Heretofore described " hydro-thermal method ", which refers to carbon source aqueous solution being fitted into reaction kettle, carries out hydro-thermal reaction, through cooling down, Be filtered, washed, dry after obtain the method for carbon ball template, the technology being known in the art specifically, is prepared using hydro-thermal method Carbon ball is typical as the operating method of template but unrestricted example has carbon disclosed in CN10324777A or CN102464304A The preparation method of ball template.
It is to use the carbon ball template being scattered in anionic metal salting liquid to synthesize in the present invention, abandons It is previous to use the operation that metal salt is dissolved in carbon ball template or carbon ball suspension.Not only anionic metal can be adsorbed by carbon ball, water OH in solution-Anion can also be adsorbed by carbon ball, and absorption of these anion in carbon ball is vied each other.This hair The bright addition sequence can be effectively prevented the OH in aqueous solution-Anion adsorbs occupy-place in advance in carbon ball, so as to promote The absorption of anionic metal, enables the anionic metal deeper into carbon ball inside, and the multiple layer metal oxide of acquisition is hollow Ball has the specific surface area of bigger.
Heretofore described " roasting " refers to that in temperature be the roasting carried out solid powder at 350-800 DEG C, this field " roasting " herein can also be replaced with calcining, heat treatment etc. by technical staff, be carried out usually in muffle furnace.
In the present invention, the preparation method of more shell-layer metal oxide hollow balls based on Anion-adsorption synthesis is specific It may comprise steps of：
(1) carbon source aqueous solution is fitted into reaction kettle and carries out hydro-thermal reaction, carbon is obtained after cooling down, being filtered, washed, dry Ball template；
(2) the carbon ball template is scattered in anionic metal salting liquid, at 20-70 DEG C after stirring and adsorbing 4-12h, Through filtering, washing, drying, solid powder material is obtained；
(3) solid powder material is roasted, more shell-layer metal oxide hollow balls is obtained after cooling.
The present invention preparation method in, before roasting can repeat " at 20-70 DEG C stir 4-12h after filter, spend from Sub- water washing 3-5 times, is put into 60-120 DEG C of baking oven dry 12-24h " this adsorption process 1-5 times, so as to obtain shell in 2- More shell-layer metal oxide hollow balls between 5 layers.
After the carbon ball template is scattered in anionic metal salting liquid in the present invention, the stirring and adsorbing at 20-70 DEG C 4-12h, for example, whipping temp for 20 DEG C, 22 DEG C, 25 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 58 DEG C, 60 DEG C, 62 DEG C, 65 DEG C, 68 DEG C, 70 DEG C, adsorption time for example can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 10.5h, 11h, 11.5h, 12h, typical but non-limiting can be stirring and adsorbing 4h at 60 DEG C, stirring and adsorbing 6h at 50 DEG C, be stirred at 70 DEG C Adsorb 12h etc..
Preparation method of the present invention by improving adsorption temp to 70 DEG C, causes precursor salt to be decomposed, is prepared The mixture of oxide hollow sphere and cubic block.
In the step (1) of the present invention, the carbon source is any one in glucose, sucrose, starch, citric acid or urea Or at least two mixture, preferably sucrose.
In the step (1) of the present invention, the selection of the anionic metal salt is same as above, and this will not be repeated here.
Preferably, described in step (1) of the present invention in carbon source aqueous solution carbon source a concentration of 0.01-5.5M, such as can be with It is 0.01M, 0.05M, 0.1M, 0.5M, 1M, 1.5M, 2M, 2.5M, 3M, 3.5M, 4M, 4.5M, 5M, 5.5M, preferably 1-5M, into One step is preferably 1.5M.
Preferably, the temperature of hydro-thermal reaction described in step (1) of the present invention is 180-200 DEG C, such as can be 180 DEG C, 182 DEG C, 185 DEG C, 188 DEG C, 190 DEG C, 192 DEG C, 195 DEG C, 198 DEG C, preferably 200 DEG C, 185-200 DEG C.
Preferably, the time of hydro-thermal reaction described in step (1) of the present invention is 120-140min, such as can be 120min, 122min, 125min, 130min, 132min, 135min, 138min, 140min, preferably 130-135min.
Preferably, washing described in step (1) of the present invention is carried out using deionized water and ethyl alcohol.
Preferably, temperature dry described in step (1) of the present invention is 60-120 DEG C, for example, can be 60 DEG C, 62 DEG C, 65 ℃、68℃、70℃、72℃、75℃、78℃、80℃、90℃、92℃、95℃、98℃、100℃、112℃、115℃、118℃、 200 DEG C, preferably 80-100 DEG C.
Preferably, the time dry described in step (1) of the present invention is 12-24h, for example, can be 12h, 14h, 15h, 16h, 18h, 20h, 22h, 23h, for 24 hours, preferably 15-24h.
In the step (2) of the present invention, a concentration of 0.01-1M of the anionic metal salting liquid, such as can be 0.01M、0.02M、0.03M、0.04M、0.05M、0.06M、0.07M、0.08M、0.09M、0.1M、0.2M、0.3M、0.4M、 0.5M, 0.7M, 0.8M, 0.9M, 1M, preferably 0.1-1M.
Preferably, sour cleaning treatment is carried out after the absorption 4-12h can also be included in step (2) of the present invention, then It is filtered again.
Preferably, the time of the sour cleaning treatment is 0.5-24h, for example, can be 0.5h, 0.8h, 1h, 3h, 5h, 8h, 10h、11h、12h、14h、15h、16h、18h、20h、22h、23h、24h。
Preferably, the acid that the sour cleaning treatment uses is any one in hydrochloric acid, sulfuric acid or acetic acid or at least two Mixture.
In the preparation method of the present invention, sour cleaning treatment is carried out before calcining.
The present invention can be removed and be sunk during high temperature adsorption since metal salt decomposes the block generated using sour cleaning treatment It forms sediment, so as to prevent mixing oxide cubic block in the oxide hollow sphere obtained after calcining, it is ensured that the uniformity of product morphology；It adopts With sour cleaning treatment, acid reacts to each other with the metal ion adsorbed in carbon ball, interacts in processing procedure, can further adjust Adsorbance and distribution of the metal ion in carbon ball.After high temperature adsorption, if not using sour cleaning treatment, obtain be hollow ball and The mixture of cubic block；It is cleaned using concentrated hydrochloric acid, can obtain the thicker single shell hollow sphere of shell wall；It is cleaned, obtained using glacial acetic acid Three shell hollow spheres thin to shell wall.
Preferably, washing described in step (2) of the present invention is carried out using deionized water, and the number of the washing is preferably 3- 5 times.
Preferably, temperature dry described in step (2) of the present invention is 60-120 DEG C, for example, can be 60 DEG C, 62 DEG C, 65 ℃、68℃、70℃、72℃、75℃、78℃、80℃、90℃、92℃、95℃、98℃、100℃、112℃、115℃、118℃、 200 DEG C, preferably 80-100 DEG C.
Preferably, the time dry described in step (2) of the present invention is 12-24h, for example, can be 12h, 14h, 15h, 16h, 18h, 20h, 22h, 23h, for 24 hours, preferably 15-24h.
In the step (3) of the present invention, the temperature of the roasting is 350-800 DEG C, for example, can be 350 DEG C, 355 DEG C, 360 ℃、370℃、380℃、400℃、420℃、450℃、480℃、500℃、550℃、600℃、620℃、650℃、700℃、 750 DEG C, preferably 800 DEG C, 400-600 DEG C.
Preferably, the heating rate of high-temperature roasting described in step (3) of the present invention is 0.5-10 DEG C/min, such as can be 0.5℃/min、1℃/min、2℃/min、3℃/min、4℃/min、5℃/min、6℃/min、7℃/min、8℃/min、9 DEG C/min, 10 DEG C/min, preferably 0.5-1 DEG C/min.
Preferably, the time roasted described in step (3) of the present invention be 0.5-10h, such as can be 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, preferably 0.5-2h.
Preferably, the atmosphere roasted described in step (3) of the present invention is air and/or oxygen, preferably oxygen.
Preparation method of the present invention, is calcined by using oxygen atmosphere, accelerates crystallization and the carbon ball of metal oxide Combustion decomposition, generate a large amount of gases impact shell walls, the internal metal oxide hollow knot with a plurality of cavities be prepared Structure.
Preparation method of the present invention repeats absorption number by increasing, increases precursor salt in carbon ball template Adsorbance and into depth, so as to generate more oxides in calcination process to support to be formed more shell numbers, And shell thickness can be increased, three thicker shell-layer metal oxide hollow balls of shell wall have been prepared.Metallic element is to carbon ball Burning has catalysed promoted effect.Absorption number is repeated to increase adsorbance of the precursor salt in carbon ball by increasing, thus into One step promotes catalysis combustion of the metallic element to carbon ball, and can promote the nucleation of metal oxide, growth so that metal oxygen The gradual long great achievement nanometer rods of compound nano particle, are prepared the oxide hollow sphere that shell wall is made of nanometer rods.
As the further optimal technical scheme of the present invention, the preparation method includes the following steps：
(1) aqueous sucrose solution of a concentration of 1.5mol/L is fitted into hydro-thermal reaction 120- in 180-200 DEG C of autoclave 140min is filtered after natural cooling, and after repeatedly washing, and product is put into 60-120 DEG C of baking oven dry 12-24h, is obtained Carbon ball template；
(2) the carbon ball template is dispersed in the anionic metal salting liquid of a concentration of 0.01-1.0mol/L, In, the anionic metal salt is any one or at least two in vanadate, manganate, molybdate, chromate or tungstates The mixture of kind, filters after stirring and adsorbing 4-12h at 20-70 DEG C, is washed with deionized 3-5 times, be put into 60-120 DEG C of baking Dry 12-24h, obtains solid powder material in case；
(3) solid powder material is placed in Muffle furnace and carries out high-temperature roasting, more shells are obtained after natural cooling Layer metallic oxide hollow sphere.
Solvent is used as water, ethyl alcohol or ethyl alcohol and water for dispersed metal anion salt solution in step (2) of the present invention Mixture, preferably using the mixture of second alcohol and water.
In the present invention by adjusting the ratio of water in solvent and ethyl alcohol, adsorption temp, repeat absorption number, at sour cleaning The synthesis conditions such as reason, calcination atmosphere, make the multiple layer metal oxide hollow sphere of synthesis have superior chemical property, make it Advantage with bigger during applied to field of lithium ion battery.
Second aspect, the present invention also provides more shell-layer metal oxides that preparation method as described in relation to the first aspect obtains Hollow ball, internal cavities are at least one, and shell wall is accumulated by metal oxide nanoparticles or nanometer rods, and shell number exists Arbitrary modulation between two to five layers, the size and shell thickness of hollow ball are controllable.
Preferably, the metal oxide being directed to is V2O5、MnO2、WO3、MoO3Or Cr2O3In it is any one Kind or at least two mixture.
By the method for the present invention prepare more shell-layer metal oxide hollow balls, shell by metal oxide nano particle Or nanometer rods composition, the metal oxide is preferably V2O5、MnO2、MoO3、Cr2O3、WO3.By controlling anionic metal The ratio of water and ethyl alcohol, adsorption temp in the concentration of salt, solvent repeat absorption number, sour cleaning treatment, calcination temperature, heating The conditions such as rate, calcination atmosphere can realize arbitrary modulation of the shell number between two layers to five layers, the internal cavities of hollow ball Number can be one or more, shell thickness 30-100nm.
The third aspect, the present invention also provides a kind of anode material for lithium-ion batteries, use the system described in first aspect More shell-layer metal oxide hollow balls that Preparation Method obtains or more shell-layer metal oxide hollow balls as described in second aspect.
Illustratively, more shell V that the present invention will can wherein synthesize2O5Hollow ball is used for anode material for lithium-ion batteries, i.e., By more shell V2O5Hollow ball, conductive agent and binding agent uniformly disperse forms slurry in a solvent, and slurry is evenly coated in aluminium foil On, it is put into 80-140 DEG C of baking oven and dries, the above-mentioned electrode slice for coating active material is cut into sequin, vacuum is done at 80 DEG C Dry 12-24h is spare, and test battery is using conventional button cell, using lithium foil as to electrode, LiPF6Organic solution be Electrolyte is assembled in glove box.
More shell V of the present invention2O5In the preparation method of hollow ball positive electrode, conductive agent can be used acetylene black or Kynoar (PVDF) or sodium carboxymethylcellulose (CMC) can be used in person's conductive black, binding agent, forms slurry solvent for use Can be N-Methyl pyrrolidone (NMP) or water；The proportioning of electrode active material slurry is：More shell V2O5Hollow ball, conductive agent and The weight ratio of binding agent is 1:(0.125~0.6):(0.125~0.4)；Slurry is applied on aluminium foil, generally through smearing 1-10 After, the quality of active material is 0.6-6mg/cm2；Lithium salts in electrolyte is LiPF6, a concentration of 1M, solvent is carbonic acid second Enester (EC) and the mixture of diethyl carbonate (DEC), weight ratio 1:1 either EC, DEC, dimethyl carbonate (DMC) it is mixed Close object, weight ratio 1:1:1.
Fourth aspect, the present invention also provides a kind of lithium ion batteries, use the lithium-ion electric as described in the third aspect Pond positive electrode is 50-2000mA/g in current density, and voltage is cycle 100 times under the conditions of the charge-discharge test of 1.5-4.0V Afterwards, specific discharge capacity 402.4-456.4mAh/g.
Illustratively, the V being prepared with the method for the invention2O5What more shell hollow sphere positive electrodes assembled Lithium ion battery is 50-2000mA/g in current density, and voltage is cycle 100 times under the conditions of the charge-discharge test of 1.5-4.0V Its specific discharge capacity is than V under the same terms afterwards2O5The specific discharge capacity of nanometer sheet positive electrode is 1.51-5.06 times high；Wherein, with Three shell V2O5The specific discharge capacity for the lithium ion battery that hollow ball assembles is up to 402.4mAh/g.
More shell V that the present invention is prepared2O5Hollow ball be used as lithium ion battery positive electrode, with it is traditional with LiCoO2、LiMn2O4、LiFePO4Materials is waited to be compared for the lithium ion battery of anode, not only specific capacity improves 2-3 times, but also Cycle performance, high rate performance are also improved greatly.With V2O5Nanometer sheet is compared, more shell V prepared by the present invention2O5Hollow ball Specific surface area with bigger, electrode material and electrolyte contacts are more preferable, lithium ion storage site is more, improve specific capacity； Meanwhile suitable more shell hollow-core constructions not only can effectively buffer electrode structure and volume change, but also can be preferably Commensurate structure force and stress, so as to significantly improve cyclical stability；In addition, the hollow ball with stephanoporate thin wall, ion with The transmission range of electronics is shorter, electrochemical reaction activity higher, transport resistance smaller, so as to improve fast charging and discharging ability.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention provides the metal oxide precursor of anionic form by anionic metal salting liquid；Using The metal ion presoma of the anionic form can not only increase its adsorbance in the synthesis process, make the anionic metal Can be deeper into carbon ball inside, and the number of plies of metallic oxide hollow sphere can be increased, make it have the specific surface of bigger Product, realizes arbitrary modulation of the shell number between 2-5 layers, shell thickness 30-100nm；
(2) more shell-layer metal oxide hollow balls that the present invention is prepared have the specific surface area of bigger, electrode material With electrolyte contacts are more preferable, lithium ion storage site is more, improve specific capacity, be used as the positive electrode of lithium ion battery When, it is 50-2000mA/g in current density, voltage is its electric discharge after recycling 100 times under the conditions of the charge-discharge test of 1.5-4.0V Specific capacity is 1.51-5.06 times higher than the specific discharge capacity of nanometer sheet positive electrode under the same terms；Wherein, with three shell metallic oxygen The specific discharge capacity for the lithium ion battery that compound hollow ball assembles is up to 402.4-456.4mAh/g, quick so as to improve Charging and discharging capabilities.
Description of the drawings
Fig. 1 is bivalve layer V prepared by embodiment 12O5The transmission electron microscope photo of hollow ball.
Fig. 2 is three shell V prepared by embodiment 22O5The transmission electron microscope photo of hollow ball.
Fig. 3 a, 3b are more shell V prepared by embodiment 1,2 respectively2O5The X-ray diffractogram of hollow ball.
Fig. 4 a, 4b, 4c, 4d are more shell MnO prepared by embodiment 3,4,5,6 respectively2、WO3、MoO3、Cr2O3Hollow ball Transmission electron microscope photo.
Fig. 5 is more shell V prepared by embodiment 1,2,3,4,5,62O5、MnO2、MoO3、Cr2O3、WO3The X ray of hollow ball Diffraction pattern.
Fig. 6 is the preparation of embodiment 1,2 with three shells, bivalve layer V2O5Hollow ball is the lithium ion battery of positive electrode Cycle performance curve (curve a, b) and embodiment 7 prepare with V2O5Nanometer sheet is followed for the lithium ion battery of positive electrode Ring performance curve (curve c) comparison diagrams.
Fig. 7 is the preparation of embodiment 8 with three shell V2O5Hollow ball is close in different electric currents for the lithium ion battery of positive electrode Under degree, the change curve of specific discharge capacity.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
For the present invention is better described, technical scheme of the present invention is easy to understand, of the invention is typical but non-limiting Embodiment is as follows：
Embodiment 1
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water repeatedly washs, product is put into 80 DEG C of baking ovens and is dried for 24 hours, about 2.7 μm of gained carbon ball diameter.
Carbon ball template is dispersed in 0.01M NH4VO3In solution.At 70 DEG C, filtered after stirring 6h, use deionized water Washing 3 times is put into 120 DEG C of baking ovens dry 12h.Then the carbon ball after absorption vanadic salts is dispersed in 0.01M NH again4VO3It is molten In liquid, above-mentioned absorption, washing, drying process 1 time are repeated, obtained solid powder is placed in Muffle furnace, is heated up with 0.5 DEG C/min To 400 DEG C, calcining at constant temperature 30min, bivalve layer V is obtained after natural cooling2O5Hollow ball, shell size are about 1.1 μm.
It is 7 by weight ratio:2:1 bivalve layer V2O5Hollow ball, acetylene black and PVDF, which are dispersed in nmp solvent, to be formed Slurry.Slurry is evenly coated on aluminium foil, after smearing 6 times repeatedly, the thickness about 3mg/cm of coating2, placed it in after coating It is dried in 80 DEG C of baking ovens.The electrode slice for coating active material is cut into a diameter of 1.6 centimetres of sequin, vacuum is done at 80 DEG C Dry 12h is spare.
Battery is tested using conventional button cell, using lithium foil as to electrode, with 1M LiPF6Organic solution be Electrolyte, mixture of the solvent for ethylene carbonate (EC) and diethyl carbonate (DEC), the two weight ratio are 1:1, in glove box In be assembled.Cycle performance test is using current constant mode, current density 1000mA/g, voltage 1.5-4.0V.Charge and discharge After cycle 100 times, specific discharge capacity is 359.0mAh g-1。
The transmission electron microscope photo of product is as shown in Figure 1, hollow ball for double shell structurres.The a curves of Fig. 3 are its X ray Diffracting spectrum, it is pure phase V that analysis, which is understood,2O5.The b curves of Fig. 6 are that its cycle performance as anode material for lithium-ion batteries is bent Line, it is known that good cycling stability.
Embodiment 2
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water repeatedly washs, product is put into 80 DEG C of baking ovens and is dried for 24 hours, about 2.7 μm of gained carbon ball diameter.
Carbon ball template is dispersed in 0.1M NH4VO3In solution.At 70 DEG C, filter, be washed with deionized water after stirring 6h It washs 3 times, is put into 60 DEG C of baking ovens and dries for 24 hours.Then the carbon ball after absorption vanadic salts is disperseed in glacial acetic acid again, after stirring 8h Centrifugation, and cleaned 2 times with deionized water, obtained solid powder is placed in Muffle furnace, is warming up to 400 DEG C with 1 DEG C/min, constant temperature 30min is calcined, three shell V of thin-walled are obtained after natural cooling2O5Hollow ball, shell size are about 1.1 μm.
It is 7 by weight ratio:2:1 three shell V of thin-walled2O5Hollow ball, acetylene black and PVDF are dispersed in nmp solvent Form slurry.Slurry is evenly coated on aluminium foil, after smearing 2 times repeatedly, the thickness about 1mg/cm of coating2, by it after coating It is placed in 80 DEG C of baking ovens and dries.The electrode slice for coating active material is cut into a diameter of 1.6 centimetres of sequin, it is true at 80 DEG C The dry 12h of sky is spare.
Battery is tested using conventional button cell, using lithium foil as to electrode, with 1M LiPF6Organic solution be Electrolyte, solvent are ethylene carbonate (EC) and diethyl carbonate (DEC), the mixture of dimethyl carbonate (DMC), and weight ratio is 1:1:1, it is assembled in glove box.Cycle performance test uses current constant mode, current density 1000mA/g, and voltage is 1.5-4.0V.After charge and discharge cycles 100 times, specific discharge capacity is 402.4mAh g-1。
The transmission electron microscope photo of product is as shown in Fig. 2, hollow ball for more shell structurres.The b curves of Fig. 3 are its X ray Diffracting spectrum, it is pure phase V that analysis, which is understood,2O5.The a curves of Fig. 6 are that its cycle performance as anode material for lithium-ion batteries is bent Line, it is known that good cycling stability.
Embodiment 3
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water and ethyl alcohol repeatedly washing, product is put into 80 DEG C of baking ovens dry 12h, about 2.7 μ of gained carbon ball diameter m。
Carbon ball template is dispersed in 0.01M K2MnO4In aqueous solution, mixture of the solvent for water and ethyl alcohol, the two body Product is than being 1:It at 3,30 DEG C, filters, is washed with deionized 3 times after stirring 12h, dry 12h is put into 80 DEG C of baking ovens, by gained Solid powder is placed in Muffle furnace, is warming up to 450 DEG C, calcining at constant temperature 2h with 5 DEG C/min, three shell MnO are obtained after natural cooling2 Hollow ball, shell size are about 1.2 μm.
The transmission electron microscope photo of product is the hollow ball of three shell structurres as shown in fig. 4 a.The a curves of Fig. 5 are its X ray Diffracting spectrum, it is pure phase MnO that analysis, which is understood,2。
Embodiment 4
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water and ethyl alcohol repeatedly washing, product is put into 80 DEG C of baking ovens dry 12h, about 2.7 μ of gained carbon ball diameter m。
Carbon ball template is dispersed in 0.2M (NH4)6W7O24·6H2In O aqueous solutions, solvent is water, at 20 DEG C, stirring It filters, is washed with deionized 3 times after 6h, be put into 80 DEG C of baking ovens dry 12h, obtained solid powder is placed in Muffle furnace, 500 DEG C, calcining at constant temperature 1h are warming up to 1 DEG C/min, four shell WO are obtained after natural cooling3Hollow ball, shell size are about 0.9 μm。
The transmission electron microscope photo of product is the hollow ball of four shell structurres as shown in Figure 4 b.The b curves of Fig. 5 are its X ray Diffracting spectrum, it is pure phase WO that analysis, which is understood,3。
Embodiment 5
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water and ethyl alcohol repeatedly washing, product is put into 80 DEG C of baking ovens dry 12h, about 2.7 μ of gained carbon ball diameter m。
Carbon ball template is dispersed in 1.0M (NH4)2MoO4In aqueous solution, solvent is water, at 20 DEG C, is taken out after stirring 6h Filter, is washed with deionized 3 times, is put into 80 DEG C of baking ovens dry 12h, obtained solid powder is placed in Muffle furnace, with 10 DEG C/ Min is warming up to 350 DEG C, calcining at constant temperature 10h, and MoO is obtained after natural cooling3Hollow ball, shell size are about 1.0 μm.
The transmission electron microscope photo of product is as illustrated in fig. 4 c.The c curves of Fig. 5 are its X ray diffracting spectrum, and it is pure that analysis, which is understood, Phase MoO3。
Embodiment 6
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 133min, after natural cooling It filters, and after water and ethyl alcohol repeatedly washing, product is put into 80 DEG C of baking ovens dry 12h, about 3.1 μ of gained carbon ball diameter m。
Carbon ball template is dispersed in 1.0M (NH4)2CrO4In aqueous solution, solvent is water, at 25 DEG C, is taken out after stirring 6h Filter, is washed with deionized 3 times, is put into 120 DEG C of baking ovens dry 12h, obtained solid powder is placed in Muffle furnace, with 1 DEG C/ Min is warming up to 500 DEG C, calcining at constant temperature 1h, and five shell Cr are obtained after natural cooling2O3Hollow ball, shell size are about 1.1 μm.
The transmission electron microscope photo of product is the hollow ball of five shell structurres as shown in figure 4d.The d curves of Fig. 5 are its X ray Diffracting spectrum, it is pure phase Cr that analysis, which is understood,2O3。
Embodiment 7
By the aqueous sucrose solution of a concentration of 1.5M in 200 DEG C of autoclave hydro-thermal reaction about 130min, after natural cooling It filters, and after water repeatedly washs, product is put into 80 DEG C of baking ovens and is dried for 24 hours, about 2.7 μm of gained carbon ball diameter.
Carbon ball template is dispersed in 0.1M NH4VO3In solution.At 70 DEG C, filter, be washed with deionized water after stirring 6h It washs 3 times, is put into 60 DEG C of baking ovens dry 12h.Then the carbon ball after absorption V salt is disperseed in glacial acetic acid again, after stirring 8h Centrifugation, and cleaned 2 times with deionized water, obtained solid powder is placed in Muffle furnace, is warming up to 400 DEG C with 1 DEG C/min, constant temperature 30min is calcined, three shell V of thin-walled are obtained after natural cooling2O5Hollow ball, shell size are about 1.1 μm.
It is 8 by weight ratio:1:1 three shell V of thin-walled2O5Hollow ball, conductive black and CMC are dispersed in aqueous solvent Form slurry.Slurry is evenly coated on aluminium foil, after smearing 2 times repeatedly, the thickness about 1mg/cm of coating2, by it after coating It is placed in 80 DEG C of baking ovens and dries.The electrode slice for coating active material is cut into a diameter of 1.6 centimetres of sequin, it is true at 80 DEG C The dry 12h of sky is spare.
Battery is tested using conventional button cell, using lithium foil as to electrode, with 1M LiPF6Organic solution be Electrolyte, solvent are ethylene carbonate (EC) and diethyl carbonate (DEC), the mixture of dimethyl carbonate (DMC), and weight ratio is 1:1:1, it is assembled in glove box.Charge-discharge test uses time-dependent current mode, and current density is gradually increased to from 50mA/g Then 200mA/g, 1000mA/g, 2000mA/g are reduced to 50mA/g again.When current density increases to 2000mA/g, discharge ratio Capacity is still up to 331.8mAh g-1, when current density is reduced to 50mA/g again, specific discharge capacity increases to 456.4mAh therewith g-1。
Embodiment 8
By the glucose solution of a concentration of 0.1M in 180 DEG C of autoclave hydro-thermal reaction about 120min, natural cooling After filter, and after water and ethyl alcohol repeatedly washing, product is put into 60 DEG C of baking ovens dry 18h, gained carbon ball diameter about 2.7 μm。
Carbon ball template is dispersed in 0.1M (NH4)2MoO4In aqueous solution, solvent is water, at 50 DEG C, is taken out after stirring 8h Filter, is washed with deionized 3 times, is put into 60 DEG C of baking ovens dry 18h, obtained solid powder is placed in Muffle furnace, with 1 DEG C/ Min is warming up to 400 DEG C, calcining at constant temperature 2h, and MoO is obtained after natural cooling3Hollow ball, shell size are about 1.0 μm.
Embodiment 9
By the amidin of a concentration of 5M in 190 DEG C of autoclave hydro-thermal reaction about 140min, take out after natural cooling Filter, and after water and ethyl alcohol repeatedly washing, product is put into 100 DEG C of baking ovens dry 20h, about 3 μm of gained carbon ball diameter.
Carbon ball template is dispersed in 0.5M (NH4)2MoO4In aqueous solution, solvent is water, at 70 DEG C, is taken out after stirring 12h Filter, is washed with deionized 3 times, is put into 80 DEG C of baking ovens dry 15h, obtained solid powder is placed in Muffle furnace, with 5 DEG C/ Min is warming up to 500 DEG C, calcining at constant temperature 8h, and MoO is obtained after natural cooling3Hollow ball, shell size are about 1.0 μm.
Embodiment 10
By the aqueous sucrose solution of a concentration of 4M in 188 DEG C of autoclave hydro-thermal reaction about 138min, take out after natural cooling Filter, and after water and ethyl alcohol repeatedly washing, product is put into 90 DEG C of baking ovens dry 20h, about 3.1 μm of gained carbon ball diameter.
Carbon ball template is dispersed in 0.6M (NH4)2CrO4In aqueous solution, solvent is water, at 25 DEG C, is taken out after stirring 8h Filter, is washed with deionized 3 times, is put into 100 DEG C of baking ovens dry 10h, obtained solid powder is placed in Muffle furnace, with 7 DEG C/ Min is warming up to 680 DEG C, calcining at constant temperature 1h, and five shell Cr are obtained after natural cooling2O3Hollow ball, shell size are about 1.1 μm.
Comparative example 1
By NH4VO3It is placed in Muffle furnace, is warming up to 400 DEG C, calcining at constant temperature 1h with 1 DEG C/min, is obtained after natural cooling V2O5Nanometer sheet, size are about 100-300nm.
It is 5 by weight ratio:3:2 V2O5Nanometer sheet, acetylene black and PVDF, which are dispersed in nmp solvent, forms slurry.It will Slurry is evenly coated on aluminium foil, after smearing 1 time repeatedly, the thickness about 0.6mg/cm of coating2, 80 DEG C of bakings are placed it in after coating It is dried in case.The electrode slice for coating active material is cut into a diameter of 1.6 centimetres of sequin, 12h is dried in vacuo at 80 DEG C It is spare.
Battery is tested using conventional button cell, using lithium foil as to electrode, with 1M LiPF6Organic solution be Electrolyte, mixture of the solvent for ethylene carbonate (EC) and diethyl carbonate (DEC), the two weight ratio are 1:1, in glove box In be assembled.Cycle performance test is using current constant mode, current density 1000mA/g, voltage 1.5-4.0V.Charge and discharge After cycle 100 times, specific discharge capacity is 79.5mAh g-1。
It can be seen from above-described embodiment that more shell-layer metal oxide hollow balls that the present invention is prepared have bigger Specific surface area, electrode material and electrolyte contacts are more preferable, lithium ion storage site is more, improve specific capacity, are used as It is 50-2000mA/g in current density, voltage is the charge-discharge test condition of 1.5-4.0V during the positive electrode of lithium ion battery Under, its specific discharge capacity is higher 1.51-5.06 than the specific discharge capacity of nanometer sheet positive electrode under the same terms after recycling 100 times Times；Wherein, the specific discharge capacity of the lithium ion battery assembled with three shell-layer metal oxide hollow balls is up to 402.4- 456.4mAh/g, so as to improve fast charging and discharging ability.
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention And the increase of accessory, selection of concrete mode etc., it all falls within protection scope of the present invention and the open scope.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (40)

  1. A kind of 1. preparation method of more shell-layer metal oxide hollow balls based on Anion-adsorption synthesis, which is characterized in that institute The method of stating includes：The carbon ball template is scattered in anionic metal salting liquid by the carbon ball prepared by the use of hydro-thermal method as template In, it is fired to obtain more shell-layer metal oxide hollow balls；
    More shell-layer metal oxide hollow balls for shell number be at least two layers, shell wall by metal oxide nanoparticles and/ Or nanometer rods accumulation forms and internal cavities are at least one spherical structure；
    The method specifically includes following steps：
    (1) carbon source aqueous solution is fitted into reaction kettle and carries out hydro-thermal reaction, carbon ball mould is obtained after cooling down, being filtered, washed, dry Plate；
    (2) the carbon ball template is scattered in anionic metal salting liquid, at 20-70 DEG C after stirring and adsorbing 4-12h, through taking out Filter, washing, drying, obtain solid powder material；
    (3) solid powder material is roasted, more shell-layer metal oxide hollow balls is obtained after cooling.
  2. 2. preparation method according to claim 1, which is characterized in that the anionic metal salt for vanadate, manganate, In molybdate, chromate or tungstates any one or at least two mixture.
  3. 3. preparation method according to claim 2, which is characterized in that the anionic metal salt is NH4VO3、K2MnO4、 (NH4)2MoO4、(NH4)2CrO4Or (NH4)6W7O24·6H2In O any one or at least two mixture.
  4. 4. preparation method according to claim 1, which is characterized in that in step (1), the carbon source for glucose, sucrose, In starch, citric acid or urea any one or at least two mixture.
  5. 5. preparation method according to claim 4, which is characterized in that in step (1), the carbon source is sucrose.
  6. 6. preparation method according to claim 1, which is characterized in that in step (1), carbon source in the carbon source aqueous solution A concentration of 0.01-5.5M.
  7. 7. preparation method according to claim 6, which is characterized in that in step (1), carbon source in the carbon source aqueous solution A concentration of 1-5M.
  8. 8. preparation method according to claim 1, which is characterized in that in step (1), the temperature of the hydro-thermal reaction is 180-200℃。
  9. 9. preparation method according to claim 8, which is characterized in that in step (1), the temperature of the hydro-thermal reaction is 185-200℃。
  10. 10. preparation method according to claim 1, which is characterized in that in step (1), the time of the hydro-thermal reaction is 120-140min。
  11. 11. preparation method according to claim 10, which is characterized in that in step (1), the time of the hydro-thermal reaction is 130-135min。
  12. 12. preparation method according to claim 1, which is characterized in that in step (1), the washing is using deionized water It is carried out with ethyl alcohol.
  13. 13. preparation method according to claim 1, which is characterized in that in step (1), the temperature of the drying is 60- 120℃。
  14. 14. preparation method according to claim 13, which is characterized in that in step (1), the temperature of the drying is 80- 100℃。
  15. 15. preparation method according to claim 1, which is characterized in that in step (1), the time of the drying is 12- 24h。
  16. 16. preparation method according to claim 15, which is characterized in that in step (1), the time of the drying is 15- 24h。
  17. 17. preparation method according to claim 1, which is characterized in that in step (2), the anionic metal salting liquid A concentration of 0.01-1M.
  18. 18. preparation method according to claim 17, which is characterized in that in step (2), the anionic metal salting liquid A concentration of 0.1-1M.
  19. 19. preparation method according to claim 1, which is characterized in that in step (2), acid is carried out after the absorption 4-12h Cleaning treatment, then filtered.
  20. 20. preparation method according to claim 19, which is characterized in that the time of the acid cleaning treatment is 0.5-24h.
  21. 21. preparation method according to claim 19, which is characterized in that the acid that uses of acid cleaning treatment for hydrochloric acid, In sulfuric acid or acetic acid any one or at least two mixture.
  22. 22. preparation method according to claim 1, which is characterized in that in step (2), the washing is using deionized water It carries out.
  23. 23. preparation method according to claim 22, which is characterized in that in step (2), the number of the washing is 3-5 It is secondary.
  24. 24. preparation method according to claim 1, which is characterized in that in step (2), the temperature of the drying is 60- 120℃。
  25. 25. preparation method according to claim 24, which is characterized in that in step (2), the temperature of the drying is 80- 120℃。
  26. 26. preparation method according to claim 1, which is characterized in that in step (2), the time of the drying is 12- 24h。
  27. 27. preparation method according to claim 26, which is characterized in that in step (2), the time of the drying is 15- 24h。
  28. 28. preparation method according to claim 1, which is characterized in that in step (3), the temperature of the roasting is 350- 800℃。
  29. 29. preparation method according to claim 28, which is characterized in that in step (3), the temperature of the roasting is 400- 600℃。
  30. 30. preparation method according to claim 1, which is characterized in that in step (3), the heating rate of the roasting is 0.5-10℃/min。
  31. 31. preparation method according to claim 30, which is characterized in that in step (3), the heating rate of the roasting is 0.5-1℃/min。
  32. 32. preparation method according to claim 1, which is characterized in that in step (3), the time of the roasting is 0.5- 10h。
  33. 33. preparation method according to claim 32, which is characterized in that in step (3), the time of the roasting is 0.5- 2h。
  34. 34. preparation method according to claim 1, which is characterized in that in step (3), the atmosphere of the roasting is air And/or oxygen.
  35. 35. preparation method according to claim 34, which is characterized in that in step (3), the atmosphere of the roasting is air Or oxygen.
  36. 36. preparation method according to claim 1, which is characterized in that the described method comprises the following steps：
    (1) aqueous sucrose solution of a concentration of 1.5M is fitted into hydro-thermal reaction 120-140min in 180-200 DEG C of autoclave, it is natural It is filtered after cooling, and after repeatedly washing, product is put into 60-120 DEG C of baking oven dry 12-24h, obtains carbon ball template；
    (2) the carbon ball template is dispersed in the anionic metal salting liquid of a concentration of 0.01-1.0M, wherein, it is described Anionic metal salt is the mixing of any one or at least two in vanadate, manganate, molybdate, chromate or tungstates Object is filtered after stirring and adsorbing 4-12h at 20-70 DEG C, is washed with deionized 3-5 times, is put into 60-120 DEG C of baking oven dry 12-24h obtains solid powder material；
    (3) solid powder material is placed in Muffle furnace and roasted, more shell metallic oxygen are obtained after natural cooling Compound hollow ball.
  37. It is 37. special according to more shell-layer metal oxide hollow balls that claim 1-36 any one of them preparation methods obtain Sign is that the internal cavities of more shell-layer metal oxide hollow balls are at least one, and shell wall is by metal oxide nano Grain or nanometer rods are accumulated, shell number arbitrary modulation between two to five layers, and the size and shell thickness of hollow ball are controllable.
  38. 38. more shell-layer metal oxide hollow balls according to claim 37, which is characterized in that the metal oxide is V2O5、MnO2、WO3、MoO3Or Cr2O3In any one or at least two mixture.
  39. 39. a kind of anode material for lithium-ion batteries, which is characterized in that it uses more shell metallic oxygen as claimed in claim 37 Compound hollow ball.
  40. 40. a kind of lithium ion battery, which is characterized in that it uses anode material for lithium-ion batteries as claimed in claim 39, It is 50-2000mA/g in current density, under the conditions of voltage is the charge-discharge test of 1.5-4.0V, after recycling 100 times, discharge specific volume It measures as 402.4-456.4mAh/g.
CN201610066853.4A 2016-01-29 2016-01-29 More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application Active CN105762349B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610066853.4A CN105762349B (en) 2016-01-29 2016-01-29 More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610066853.4A CN105762349B (en) 2016-01-29 2016-01-29 More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105762349A CN105762349A (en) 2016-07-13
CN105762349B true CN105762349B (en) 2018-06-12

Family

ID=56342769

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610066853.4A Active CN105762349B (en) 2016-01-29 2016-01-29 More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105762349B (en)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106344925B (en) * 2016-08-25 2019-04-16 郑州大学 A kind of Mn2+Donor and chloroquine class drug cotransport the preparation and application of system
CN106517311B (en) * 2016-11-22 2018-06-05 南京大学昆山创新研究院 A kind of preparation method of gallic acid zinc bivalve layer nano-hollow ball
CN107742587B (en) * 2017-09-29 2019-08-13 江苏科技大学 A kind of three layers of Mn of height ratio capacity2O3@MoS2Nano-hollow ball electrode material and the preparation method and application thereof
CN108039486A (en) * 2017-12-20 2018-05-15 湖南工业大学 The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method
CN109755541B (en) * 2019-03-07 2020-11-27 肇庆市华师大光电产业研究院 Sodium-sulfur battery positive electrode material and preparation method thereof
CN109755543B (en) * 2019-03-07 2020-12-11 肇庆市华师大光电产业研究院 Sodium-ion battery negative electrode material and preparation method thereof
CN109755544B (en) * 2019-03-07 2020-12-11 肇庆市华师大光电产业研究院 Lithium-sulfur battery positive electrode material and preparation method thereof
CN111977629A (en) * 2019-05-21 2020-11-24 中国科学院宁波材料技术与工程研究所 Synthetic method for coating carbon spheres with tungsten nitride and generating tungsten nitride nanorods in situ on carbon spheres
CN110921714B (en) * 2019-11-29 2021-12-21 华南理工大学 Iron molybdate hollow microsphere, preparation thereof and application thereof in sodium-ion battery
CN113336215A (en) * 2020-03-02 2021-09-03 赵昆 Preparation method and application of monodisperse hydrothermal carbon spheres
CN113363434B (en) * 2021-05-12 2022-06-14 中国科学院过程工程研究所 Multi-core multi-shell hollow material for encapsulating nano particles and preparation method and application thereof
CN113921780A (en) * 2021-09-10 2022-01-11 中国科学院过程工程研究所 Multi-shell coated composite hollow structure material and preparation method and application thereof
CN114291846A (en) * 2021-11-19 2022-04-08 攀钢集团研究院有限公司 Preparation method of nano vanadium pentoxide cathode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464304A (en) * 2010-11-12 2012-05-23 中国科学院过程工程研究所 Multi-shell-layer metal oxide hollow ball and preparation method thereof
CN103247777A (en) * 2013-05-03 2013-08-14 中国科学院过程工程研究所 Cobaltosic oxide multi-shell hollow sphere cathode material for lithium ion battery and preparation method thereof
CN104993116A (en) * 2015-05-18 2015-10-21 陕西科技大学 Preparation method of self-assembled lithium ion battery positive material V2O5

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464304A (en) * 2010-11-12 2012-05-23 中国科学院过程工程研究所 Multi-shell-layer metal oxide hollow ball and preparation method thereof
CN103247777A (en) * 2013-05-03 2013-08-14 中国科学院过程工程研究所 Cobaltosic oxide multi-shell hollow sphere cathode material for lithium ion battery and preparation method thereof
CN104993116A (en) * 2015-05-18 2015-10-21 陕西科技大学 Preparation method of self-assembled lithium ion battery positive material V2O5

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"General synthesis of hollow MnO2、Mn3O4 and MnO nanosphere as superior anode materials for lithium ion batterues";Jie yue et al.;《Journal of Materials Chenmistry A》;20141107;第2卷(第41期);第17422页 Experimental section *

Also Published As

Publication number Publication date
CN105762349A (en) 2016-07-13

Similar Documents

Publication Publication Date Title
CN105762349B (en) More shell-layer metal oxide hollow balls based on Anion-adsorption synthesis and its preparation method and application
CN110380024B (en) Sodium transition metal oxide with P3 structure, preparation method thereof and sodium ion battery
CN101562245B (en) Method for modifying high-rate lithium-rich anode material
CN105870438B (en) A kind of lithium secondary battery lithium-rich anode composite material and preparation method
CN106960955B (en) The ternary cathode material of lithium ion battery and preparation method thereof of vanadium sulfide cladding
CN110943213B (en) MOF-derived porous carbon box loaded with Co 3 V 2 O 8 Composite negative electrode material and preparation method and application thereof
CN114204004A (en) Positive electrode material and preparation method thereof, positive plate and sodium ion battery
JP2004519082A (en) Positive electrode active material for high performance lithium secondary battery and method for producing the same
CN106711441B (en) A kind of 5V anode material for lithium-ion batteries and preparation method thereof, a kind of lithium ion battery
CN103247777A (en) Cobaltosic oxide multi-shell hollow sphere cathode material for lithium ion battery and preparation method thereof
CN106207158B (en) The preparation method of rich lithium manganate cathode material for lithium
CN106384813A (en) Fast synthesis method of positive electrode material for lithium ion battery
CN107910542A (en) A kind of lithium-rich manganese-based composite positive pole and preparation method thereof
CN109509874A (en) A kind of preparation method of molybdenum trioxide cladding lithium-rich manganese-based anode material
CN110364716A (en) Spherical magnesia coated lithium ion battery tertiary cathode material of magnesium-based MOF and preparation method thereof
CN108376776A (en) A kind of alternate core-shell structure ternary electrode material of lithium battery of height nickel and preparation method
CN109980215A (en) A kind of core-shell structure lithium-rich manganese-based anode material and preparation method thereof
CN106910881A (en) Metatitanic acid lithium coats the preparation method of nickel cobalt lithium aluminate cathode material
Kong et al. Synthesis of lithium rich layered oxides with controllable structures through a MnO2 template strategy as advanced cathode materials for lithium ion batteries
CN112499631A (en) Fe3C/C composite material and application thereof
CN106025216A (en) Positive electrode material for lithium-sulfur battery, preparation method of positive electrode material and lithium-sulfur battery
CN108598439A (en) A kind of preparation method of tungstic acid/graphene composite negative pole
CN107768628B (en) Lithium ion battery anode material and preparation method thereof
CN102569808B (en) Modification method of high-rate lithium-rich cathode material
CN112928267A (en) Composite lithium-rich cathode material and preparation method and application thereof

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
TR01 Transfer of patent right

Effective date of registration: 20230407

Address after: Room 1202, 11th Floor, Building 3, No. 88 Kechuang 6th Street, Beijing Economic and Technological Development Zone, Daxing District, Beijing, 101100

Patentee after: Zhongke Huisheng (Beijing) Pharmaceutical Technology Co.,Ltd.

Address before: 100190 No. two, No. 1, North Haidian District, Beijing, Zhongguancun

Patentee before: Institute of Process Engineering, Chinese Academy of Sciences

TR01 Transfer of patent right