CN102502889A - Co3O4 microsphere flower-like material as well as preparation method and application thereof - Google Patents

Co3O4 microsphere flower-like material as well as preparation method and application thereof Download PDF

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CN102502889A
CN102502889A CN2011103197126A CN201110319712A CN102502889A CN 102502889 A CN102502889 A CN 102502889A CN 2011103197126 A CN2011103197126 A CN 2011103197126A CN 201110319712 A CN201110319712 A CN 201110319712A CN 102502889 A CN102502889 A CN 102502889A
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flower
microballoon
solvent
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shaped
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刘艳
武英
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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Abstract

The invention discloses a Co3O4 microsphere flower-like material as well as a preparation method and application thereof. The preparation method comprises the steps of: mixing a cobalt salt, a surfactant, a precipitator and a solvent according to a stoichiometric ratio, transferring the mixed solution to a reaction kettle, carrying out hydrothermal reaction at the temperature of 95-105 DEG C for 3.5-4.5 hours, washing, drying to obtain a powdery mixed precursor, and carrying out heat treatment in air to finally obtain the Co3O4 microsphere flower-like material. The obtained Co3O4 microsphere flower-like material has better electrochemical behaviors, and can be used for negative electrodes of rechargeable lithium ion cells.

Description

A kind of Co 3O 4The flower-shaped material of microballoon
Technical field
The present invention relates to a kind of Co that is used for lithium ion battery negative material 3O 4Flower-shaped material of microballoon and preparation method thereof.
Technical background
Lithium ion battery becomes the main power supply of present electricinstallation because of its high-energy-density receives much concern.As a kind of novel battery material, the transition metal oxide that began to research and develop in 2000 more and more receives people's attention [1] because of its high energy density.Co wherein 3O 4It is a phase the most stable in the transition metal oxide family.
Co 3O 4Be typical p type, semiconductor material, bandwidth is 1.48
Figure 2011103197126100002DEST_PATH_IMAGE001
2.19 between the eV, have good electrochemical behavior and higher specific volume value, thereby obtain broad research as lithium ion battery negative material.There have been a lot of methods to prepare Co now 3O 4, such as thermal decomposition method [2], polyvalent alcohol method [3], electrochemical deposition (ECD) [4], melting salt method [5], salt solustion mehtod [6], electrochemical vapour deposition (EVD) [7], electrochemistry spray pyrolysis [8] etc.
Above-mentioned the whole bag of tricks is to Co 3O 4The electrode materials structure nanoization is improved its storage lithium performance, and still, problems such as the reunion of the particle of this material in charge and discharge process, structural stability difference have caused shortcoming such as the irreversible first inefficiency, cyclical stability difference of this material to be still waiting to solve.The present invention provides a kind of new micro nano structure flower-shaped Co in order to solve existing technical problem just 3O 4Preparation methods, emphasis is considered Co 3O 4The size and the floriform appearance of material influence electrochemical behavior, and then solve Co 3O 4The reunion of the particle of material in charge and discharge process, the problem of structural stability difference.
Consider aspect preparation method and cost, compare with above method that the micro emulsion method is because of its special preparation characteristic, such as big relatively interface, ultralow IT has been widely used and has prepared nano structural material.Microemulsion in the micro emulsion method belongs to thermodynamic stable system, under certain condition, has maintenance and stablizes undersized characteristic, has special advantages in single the dispersion in the powder preparing.In mixing process, because exchange of substance in the microemulsion takes place in the micelle collision, various chemical reactions (oxidation-reduction reaction, precipitin reaction etc.) carry out nucleation and growth in water/oily equilibrium system, and size of particles can be controlled.Because reactant is supplied with the high dispersing state, can effectively prevent and treat the local supersaturation of reactant, particle nucleation and growth process are evenly carried out.It is stable that the particle that generates keeps in water/oily equilibrium system, can not cause unnecessary cohesion.Therefore, on control particle size, pattern, the nano structural material [9-10] that the micro emulsion method can preparation be evenly distributed, percent crystallinity is high in lesser temps, less reaction times.
Reference
[1]?S.?Kobayashi,?Y.?Uchimoto.?Lithium?ion?phase-transfer?reaction?at?the?interface?between?the?lithium?manganese?oxide?electrode?and?the?nonaqueous?electrolyte.?J.?Phys.?Chem.?B,?2005,?109:?13322~13326.
[2]?X.W.?Lou,?D.?Deng,?J.Y.?Lee,?et?al.?Thermal?formation?of?mesoporous?single-crystal?Co 3O 4?nano-needles?and?their?lithium?storage?properties.?J.?Mater.?Chem.,?2008,?18:?4397~4401.
[3]?A.M.?Cao,?J.S.?Hu,?L.J.?Wan,?et?al.?Hierarchically?structured?cobalt?oxide?(Co 3O 4):?the?morphology?control?and?its?potential?in?sensors.?J.?Phys.?Chem.?B,?2006,?110:?15858~15863.
[4]?C.N.?Polo?da?Fonseca,?M.A.?de?Paoli,?A.?Gorenstein.?The?electrochromic?effect?in?cobalt?oxide?thin?films.?Adv.?Mater.,?1991,?3:?553~555.
[5]Y.K.?Liu,?G.H.?Wang,?C.K.?Xu,?et?al.?Fabrication?of?Co 3O 4?nanorods?by?calcination?of?precursor?powders?prepared?in?a?novel?inverse?microemulsion.?Chem.?Commun.,?2002,?14:?1486~1487.
[6]R.?Xu,?H.C.?Zeng.?Mechanistic?investigation?on?salt-mediated?formation?of?free-standing?Co 3O 4?nanocubes?at?95? oC.?J.?Phys.?Chem.?B.,?2003,?107:?926~930.
[7]?T.?Maruyama,?S.?Arai.?Electrochromic?properties?of?cobalt?oxide?thin?films?prepared?by?chemical?vapor?deposition.?J.?Electrochem.?Soc.,?1996,?143:?1383~1386.
[8]?D.Y.?Kim,?S.H.?Ju,?H.Y.?Koo,?et?al.?Synthesis?of?nanosized?Co 3O 4?particles?by?spray?pyrolysis.?J.?Alloy.?Compd.,?2006,?417:?254~258.
[9]?L.F.?Gou,?C.J.?Murphy.?Solution-phase?synthesis?of?Cu 2O?nanocubes.?Nano?Lett.,?2003,?3:?231~234.
?[10]?M.H.?Cao,?C.W.?Hu,?Y.H.?Wang,?et?al.?A?controllable?synthetic?route?to?Cu,?Cu 2O,?and?CuO?nanotubes?and?nanorods.?Chem.?Commun.,?2003,?15:?1884~1885。
Summary of the invention
One of the object of the invention provides a kind of Co of even grain size 3O 4The flower-shaped material of microballoon.
Two of the object of the invention provides above-mentioned a kind of Co 3O 4The flower-shaped preparation methods of microballoon.
Three of the object of the invention provides above-mentioned a kind of Co 3O 4The flower-shaped material of microballoon is as the application method of the negative material of lithium cell.
Technical scheme of the present invention
A kind of Co 3 O 4 The flower-shaped preparation methods of microballoon
A kind of Co 3O 4The flower-shaped preparation methods of microballoon, this method comprises the steps:
(1), with stir after cobalt salt, tensio-active agent, precipitation agent and the solvent 30
Figure 832428DEST_PATH_IMAGE001
60min; Carry out hydro-thermal reaction in the autoclave with whole mixing solutions immigration inner liner polytetrafluoroethylene; The control hydrothermal temperature be 95
Figure 338496DEST_PATH_IMAGE001
105 ℃; Preferred 100 ℃; Time be 3.5
Figure 554714DEST_PATH_IMAGE001
4.5h, reaction solution;
Wherein said cobalt salt is a kind of in Xiao Suangu, cobaltous acetate, cobaltous carbonate or the cobalt oxalate, is preferably Xiao Suangu;
Said tensio-active agent is cetyl trimethyl ammonia bromide (CTAB);
Described precipitation agent is urea (Co (NH 2) 2);
Described solvent is water, Pentyl alcohol and hexanaphthene; Wherein the ratio of mixture of solvent is calculated by volume; Be water: Pentyl alcohol: hexanaphthene be 18
Figure 499536DEST_PATH_IMAGE001
31.3:1:20, be preferably 28:1:20;
The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is that 1.82:1:7.27:545.45
Figure 852020DEST_PATH_IMAGE001
949.09 calculates; The ratio of mixture of preferred cobalt salt, tensio-active agent, precipitation agent and solvent is cobalt salt in molar ratio: tensio-active agent: precipitation agent: the water in the solvent is preferably 1.82:1:7.27:848.48;
The hydro-thermal reaction time is preferably 4h;
Filling degree in the autoclave be 60 80%, be preferably 75%;
(2), washing and oven dry obtain the powder-mixed presoma;
Carry out the reaction solution of step (1) gained centrifugal; Centrifugal process control centrifugal rotational speed be 3000
Figure 294820DEST_PATH_IMAGE001
3500r/min; Time be 20 30min; Oven dry after solid substance behind gained centrifugal respectively washs 3 times with deionized water and absolute ethyl alcohol, the powder-mixed presoma;
The deionized water that wherein each washing is used and the amount of absolute ethyl alcohol are by reaction solution: the volume ratio of deionized water is 1:50, and by reaction solution: the volume ratio of absolute ethyl alcohol is 1:1.5;
Wherein said oven dry; Controlled temperature be 60
Figure 188006DEST_PATH_IMAGE001
90 ℃, be preferably 70
Figure 98194DEST_PATH_IMAGE001
80 ℃;
(3), with the thermal treatment under air atmosphere of powder-mixed presoma, title product
Is 290 with the powder-mixed presoma of step (2) gained in temperature
Figure 23424DEST_PATH_IMAGE001
310 ℃, be preferably thermal treatment 3h under 300 ℃ of conditions, promptly get a kind of Co 3O 4The flower-shaped material of microballoon.
A kind of Co 3 O 4 The flower-shaped material of microballoon
Above-mentioned a kind of Co 3O 4The Co of the hydrothermal preparing process gained of the flower-shaped material of microballoon 3O 4The flower-shaped material of microballoon, this material grains size are 2 evenly and basically
Figure 247732DEST_PATH_IMAGE001
5
Figure 2011103197126100002DEST_PATH_IMAGE002
M.
Also have 20,40 60 and 80mA in addition
Figure 2011103197126100002DEST_PATH_IMAGE003
g -1Under the different charge-discharge mechanisms, the capability retention behind charge and discharge cycles 40 circles has embodied electrochemical stability and cycle life preferably more than 97%.
Above-mentioned a kind of Co 3 O 4 The application as the chargeable lithium ion battery negative material of the flower-shaped material of microballoon
Above-mentioned a kind of Co 3O 4The flower-shaped material of microballoon is used for the chargeable lithium ion battery negative material, like lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium and three fluorocarbons sulfonic acid lithium (LiPF 6, LiClO 4, LiAsF 6And CF 3SO 3Li) etc. be electrolytical chargeable lithium ion battery.
Above-mentioned a kind of Co 3O 4The flower-shaped material of microballoon is the preparation method of tricobalt tetroxide electrode negative material as the negative material of chargeable lithium ion battery, promptly adopts the coating method preparation, and its concrete steps are following:
Pressing mass ratio to cobaltosic oxide nano flaky material, acetylene black and sticker calculates; Be the cobaltosic oxide nano flaky material: acetylene black: sticker is 80:15:5; Nano-sheet material, acetylene black and sticker are mixed and be dissolved in the N-Methyl pyrrolidone (NMP); Be coated on the nickel screen collector of handling,, promptly get tricobalt tetroxide electrode negative material in 100 ℃ in vacuum, baking 12h;
Described sticker is PVDF (PVDF).
With above-mentioned gained tricobalt tetroxide electrode negative material is negative pole, and metal lithium sheet is anodal, and Vestolen PP 7052 (PP) is as the barrier film between the positive and negative electrode, 1 M LiPF 6And ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solution of 50:50 (w/w) are electrolytic solution; In the glove box of argon shield, be assembled into battery, under Land battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), carry out the constant current charge-discharge test.Voltage range is 0.01
Figure 705301DEST_PATH_IMAGE001
3.0 V Vs.Li/Li +
Beneficial effect of the present invention
A kind of Co of the present invention 3O 4The flower-shaped material of microballoon is owing to add tensio-active agent cetyl trimethyl ammonia bromide (CTAB) and precipitation agent urea (Co (NH in the preparation process in presoma 2) 2), urea is a kind of weakly alkaline material, is used to provide OH -Ion, cetyl trimethyl ammonia bromide (CTAB) serves as soft template as tensio-active agent in reaction process, be used under water/oily microenvironment, adsorbing and disperseing nucleus.Again because Pentyl alcohol, hexanaphthene and water coexistence.Can order about down in system's minimum, nanofiber nucleation, growth, reunion form spherical.
The present invention adopts the micro emulsion method, utilizes water, Pentyl alcohol (C 5H 12O), hexanaphthene (C 6H 12) with the elasticity of flexure of CTAB acting in conjunction control pattern upper layer, finally obtain Co 3O 4The flower-shaped negative material of microballoon.Because microemulsion belongs to thermodynamic stable system, under certain condition, have maintenance and stablize undersized characteristic, have special advantages in single the dispersion in the powder preparing.And because reactant is supplied with the high dispersing state, can effectively prevent and treat the local supersaturation of reactant, particle nucleation and growth process are evenly carried out.It is stable that the particle that generates keeps in water/oily equilibrium system, can not cause unnecessary cohesion, help in lesser temps, less reaction times, preparing be evenly distributed, Co that percent crystallinity is high 3O 4The flower-shaped negative material of microballoon.
Co of the present invention 3O 4The flower-shaped negative material of microballoon has electrochemical behavior preferably.This special construction has increased specific surface area, shortens e -And Li +Conducting path, thereby improve multiplying power property.Water in cobalt salt, precipitation agent, tensio-active agent, the solvent is respectively the Co that the 1.82:1:7.27:848.48 hydrothermal method makes in molar ratio 3O 4Electrode materials, 20,40,60 and 80mA
Figure 989652DEST_PATH_IMAGE003
g -1Under the different charge-discharge mechanisms, the capability retention behind charge and discharge cycles 40 circles is more than 97%, embodied preferably all characteristics such as even easy batch process of electrochemical stability and cycle life, nanoparticle size.
Description of drawings
The Co of Fig. 1, embodiment 1 gained 3O 4The SEM figure of material;
The Co of Fig. 2, embodiment 2 gained 3O 4The SEM figure of material;
The Co of Fig. 3, embodiment 3 gained 3O 4The SEM figure of material;
The Co of Fig. 4, embodiment 4 gained 3O 4The SEM figure of material;
The Co of Fig. 5, embodiment 5 gained 3O 4The SEM figure of material;
The Co of Fig. 6, embodiment 1 gained 3O 4The cycle life figure of material discharge process under the different electric flow density;
The Co of Fig. 7, embodiment 2 gained 3O 4The cycle life figure of material discharge process under the different electric flow density;
The Co of Fig. 8, embodiment 3 gained 3O 4The cycle life figure of material discharge process under the different electric flow density;
The Co of Fig. 9, embodiment 4 gained 3O 4The cycle life figure of material discharge process under the different electric flow density;
The Co of Figure 10, embodiment 5 gained 3O 4The cycle life figure of material discharge process under the different electric flow density;
The Co of Figure 11, embodiment 1 gained 3O 4The cycle life figure of material process of charging under the different electric flow density;
The Co of Figure 12, embodiment 2 gained 3O 4The cycle life figure of material process of charging under the different electric flow density;
The Co of Figure 13, embodiment 3 gained 3O 4The cycle life figure of material process of charging under the different electric flow density;
The Co of Figure 14, embodiment 4 gained 3O 4The cycle life figure of material process of charging under the different electric flow density;
The Co of Figure 15, embodiment 5 gained 3O 4The cycle life figure of material process of charging under the different electric flow density.
Embodiment
Below through embodiment and combine accompanying drawing that the present invention is further set forth, but do not limit the present invention.
Embodiment 1
Get 1.47g Xiao Suangu (Co (NO 3) 2 6H 2O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 1.2g urea (Co (NH 2) 2, analytical pure, Shanghai hundred million chemical reagent ltds of a specified duration), 1g cetyl trimethyl ammonia bromide (CTAB, analytical pure, Shanghai chemical reagents corporation) is dissolved in by 1.5ml Pentyl alcohol (C 5H 12O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 30ml hexanaphthene (C 6H 12Analytical pure; Chemical reagents corporation of traditional Chinese medicines group) and in the mixed solution formed of 27 ml deionized waters; The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:545.45, and whole adition process is carried out under magnetic agitation (81-2 type, Shanghai Si Le Instr Ltd.).After stirring 30min, whole mixing solutions is moved in the autoclave (100ml is just believing instrument plant) of inner liner polytetrafluoroethylene, the filling degree is 60%, and (95 ℃) react 3.5h at a certain temperature, and naturally cooling gets reaction solution then;
With above-mentioned reaction solution spinning; The control centrifugal rotational speed is 3000r/min; Time is 20min, and the solid substance behind gained centrifugal successively respectively washs 3 times with deionized water and absolute ethyl alcohol, uses 1000ml deionized water and 30ml absolute ethyl alcohol (analytical pure respectively at every turn; Shanghai development chemical industry one factory), wash back oven dry under 60 ℃ and obtained the powder-mixed presoma;
With the powder-mixed presoma under air atmosphere, 290 ℃ of thermal treatment 3h, final Co 3O 4Material.
The Co of gained 3O 4The SEM of material (Leo 1430 VP, German LEO company) figure sees Co shown in Figure 1, as can be seen from Figure 1 prepared 3O 4Material presents sphere, and microballoon is to be formed by a lot of nanofiber self-assemblies, and spherical diameter is 2
Figure 226916DEST_PATH_IMAGE001
5
Figure 408498DEST_PATH_IMAGE002
About m, the small-particle agglomeration appears in the part spherome surface.
Embodiment 2
Get 1.47 g Xiao Suangu (Co (NO 3) 2
Figure 863750DEST_PATH_IMAGE003
6H 2O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 1.2g urea (Co (NH 2) 2, analytical pure, Shanghai hundred million chemical reagent ltds of a specified duration), 1g cetyl trimethyl ammonia bromide (CTAB, analytical pure, Shanghai chemical reagents corporation) is dissolved in by 1.5ml Pentyl alcohol (C 5H 12O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 30ml hexanaphthene (C 6H 12, analytical pure, chemical reagents corporation of traditional Chinese medicines group) and the mixed solution formed of 47 ml deionized waters in; The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:949.09, and whole adition process is carried out under magnetic agitation (81-2 type, Shanghai Si Le Instr Ltd.); After stirring 30min, whole mixing solutions is moved in the autoclave (100ml is just believing instrument plant) of inner liner polytetrafluoroethylene; The filling degree is 80%; (105 ℃) react 4.5h at a certain temperature, and naturally cooling gets reaction solution then;
With above-mentioned reaction solution spinning; The control centrifugal rotational speed is 3200r/min; Time is 20min, and the solid substance behind gained centrifugal successively respectively washs 3 times with deionized water and absolute ethyl alcohol, uses 1333.3ml deionized water and 40ml absolute ethyl alcohol (analytical pure respectively at every turn; Shanghai development chemical industry one factory), wash back oven dry under 90 ℃ and obtained the powder-mixed presoma;
With the powder-mixed presoma under air atmosphere, 310 ℃ of thermal treatment 3h, final Co 3O 4Material.
The Co of gained 3O 4The SEM of material (Leo 1430 VP, German LEO company) figure sees Co shown in Figure 2, as can be seen from Figure 2 prepared 3O 4Material presents sphere, and microballoon is to be formed by a lot of nanofiber self-assemblies, and spherical diameter is 2
Figure 825890DEST_PATH_IMAGE001
5 About m, the small-particle agglomeration appears in the part spherome surface.
Embodiment 3
Get 1.47g Xiao Suangu (Co (NO 3) 2 6H 2O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 1.2g urea (Co (NH 2) 2, analytical pure, Shanghai hundred million chemical reagent ltds of a specified duration), 1g cetyl trimethyl ammonia bromide (CTAB, analytical pure, Shanghai chemical reagents corporation) is dissolved in by 1.5ml Pentyl alcohol (C 5H 12O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 30ml hexanaphthene (C 6H 12, analytical pure, chemical reagents corporation of traditional Chinese medicines group) and the mixed solution formed of 42ml deionized water in; The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:848.48, and whole adition process is carried out under magnetic agitation (81-2 type, Shanghai Si Le Instr Ltd.); After stirring 30min, whole mixing solutions is moved in the autoclave (100ml is just believing instrument plant) of inner liner polytetrafluoroethylene; The filling degree is 75%; (100 ℃) react 4h at a certain temperature, and naturally cooling gets reaction solution then;
With above-mentioned reaction solution spinning; The control centrifugal rotational speed is 3500r/min; Time is 30min, and the solid substance behind gained centrifugal successively respectively washs 3 times with deionized water and absolute ethyl alcohol, uses 1250ml deionized water and 37.5ml absolute ethyl alcohol (analytical pure respectively at every turn; Shanghai development chemical industry one factory), wash back oven dry under 80 ℃ and obtained the powder-mixed presoma;
With the powder-mixed presoma under air atmosphere, 300 ℃ of thermal treatment 3h, final Co 3O 4Material.
The Co of gained 3O 4The SEM of material (Leo 1430 VP, German LEO company) figure sees Co shown in Figure 3, as can be seen from Figure 3 prepared 3O 4Material microballoon uniform distribution, the ball surface is fibrous by regular nanometer sheet, and nanofiber is interconnected, and uniform distribution forms microballoon, and microsphere diameter is 2
Figure 116560DEST_PATH_IMAGE001
5
Figure 503679DEST_PATH_IMAGE002
About m.
Embodiment 4
Get 1.47g Xiao Suangu (Co (NO 3) 2
Figure 607901DEST_PATH_IMAGE003
6H 2O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 1.2g urea (Co (NH 2) 2, analytical pure, Shanghai hundred million chemical reagent ltds of a specified duration), 1g cetyl trimethyl ammonia bromide (CTAB, analytical pure, Shanghai chemical reagents corporation) is dissolved in by 1.5ml Pentyl alcohol (C 5H 12O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 30ml hexanaphthene (C 6H 12, analytical pure, chemical reagents corporation of traditional Chinese medicines group) and the mixed solution formed of 42ml deionized water in; The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:848.48, and whole adition process is carried out under magnetic agitation (81-2 type, Shanghai Si Le Instr Ltd.); After stirring 30min, whole mixing solutions is moved in the autoclave (100ml is just believing instrument plant) of inner liner polytetrafluoroethylene; The filling degree is 75%; (105 ℃) react 4.5h at a certain temperature, and naturally cooling gets reaction solution then;
With above-mentioned reaction solution spinning; The control centrifugal rotational speed is 3500r/min; Time is 20min, and the solid substance behind gained centrifugal successively respectively washs 3 times with deionized water and absolute ethyl alcohol, uses 1250ml deionized water and 37.5ml absolute ethyl alcohol (analytical pure respectively at every turn; Shanghai development chemical industry one factory), wash back oven dry under 70 ℃ and obtained the powder-mixed presoma;
With the powder-mixed presoma under air atmosphere, 300 ℃ of thermal treatment 3h, final Co 3O 4Material.
The Co of gained 3O 4The SEM of material (Leo 1430 VP, German LEO company) figure sees Co shown in Figure 4, as can be seen from Figure 4 prepared 3O 4Material presents sphere, and microballoon is to be formed by a lot of nanofiber self-assemblies, and spherical diameter is 2
Figure 826393DEST_PATH_IMAGE001
5
Figure 623448DEST_PATH_IMAGE002
About m, the small-particle agglomeration appears in the part spherome surface.
Embodiment 5
Get 1.47g Xiao Suangu (Co (NO 3) 2
Figure 232284DEST_PATH_IMAGE003
6H 2O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 1.2g urea (Co (NH 2) 2, analytical pure, Shanghai hundred million chemical reagent ltds of a specified duration), 1g cetyl trimethyl ammonia bromide (CTAB, analytical pure, Shanghai chemical reagents corporation) is dissolved in by 1.5ml Pentyl alcohol (C 5H 12O, analytical pure, chemical reagents corporation of traditional Chinese medicines group), 30ml hexanaphthene (C 6H 12, analytical pure, chemical reagents corporation of traditional Chinese medicines group) and the mixed solution formed of 42ml deionized water in; The ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent cobalt salt in molar ratio wherein: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:848.48, and whole adition process is carried out under magnetic agitation (81-2 type, Shanghai Si Le Instr Ltd.); After stirring 30min, whole mixing solutions is moved in the autoclave (100ml is just believing instrument plant) of inner liner polytetrafluoroethylene; The filling degree is 75%; (95 ℃) react 3.5h at a certain temperature, and naturally cooling gets reaction solution then;
With above-mentioned reaction solution spinning; The control centrifugal rotational speed is 3500r/min; Time is 25min, and the solid substance behind gained centrifugal successively respectively washs 3 times with deionized water and absolute ethyl alcohol, uses 1250ml deionized water and 37.5ml absolute ethyl alcohol (analytical pure respectively at every turn; Shanghai development chemical industry one factory), wash back oven dry under 70 ℃ and obtained the powder-mixed presoma;
With the powder-mixed presoma under air atmosphere, 300 ℃ of thermal treatment 3h, final Co 3O 4Material.
The Co of gained 3O 4The SEM of material (Leo 1430 VP, German LEO company) figure sees Co shown in Figure 5, as can be seen from Figure 5 prepared 3O 4Material presents sphere, and microballoon is to be formed by a lot of nanofiber self-assemblies, and spherical diameter is 2
Figure 468093DEST_PATH_IMAGE001
5
Figure 478774DEST_PATH_IMAGE002
About m, the small-particle agglomeration appears in the part spherome surface.
Application implementation example 1
The preparation of tricobalt tetroxide electrode negative material, step is following:
By quality than tricobalt tetroxide material: acetylene black (cell-grade; Xiang Tan Battery Plant): sticker (PVDF (PVDF); Analytical pure; Chemical reagents corporation of traditional Chinese medicines group) is 80:15:5; Embodiment 1
Figure 446730DEST_PATH_IMAGE001
5 prepared tricobalt tetroxide material, acetylene black and stickers are mixed respectively and are dissolved in the N-Methyl pyrrolidone (Shanghai chemical reagent purchase and supply does not have the couplet chemical plant for NMP, CP); Be coated in through acetone (analytical pure; Shanghai development chemical industry one factory) on the nickel screen collector (11 millimeters of diameters, Beijing Non-Fervoous Metal Inst.) that ultrasonic 10min and 100 ℃ of drying treatment are crossed, coating thickness is 0.2mm; In 100 ℃ in vacuum, baking 12h, obtain the corresponding tricobalt tetroxide electrode negative material of processing by embodiment 1 ~ 5 prepared tricobalt tetroxide material.
Tricobalt tetroxide electrode negative material with above-mentioned gained is a negative pole respectively, and metal lithium sheet (Beijing Non-Fervoous Metal Inst. (purity 99.9%)) is anodal, and Vestolen PP 7052 (PP, technical grade, Oil of Shanghai Petrochemical Company Company products) is as the barrier film between the positive and negative electrode, 1 M LiPF 6And ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solution of 50:50 (w/w) are electrolytic solution (Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City); Glove box (ZKX type in argon shield; Nanjing Univ. Instrument Factory) lining is assembled into battery, under Land battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), carries out the constant current charge-discharge test respectively.Voltage range is 0.01
Figure 605179DEST_PATH_IMAGE001
3.0V Vs.Li/Li +Current density is 20,40,60 and 80mA
Figure 51204DEST_PATH_IMAGE003
g -1Test environment is 25 ℃ of constant temperature.Experimental data is like Fig. 6
Figure 181971DEST_PATH_IMAGE001
shown in 15.
Can find out from Fig. 6 ~ 15,20,40,60 and 80mA
Figure 383145DEST_PATH_IMAGE003
g -1Under the different charge-discharge mechanisms, embodiment 1,2,3,4 and embodiment 5 have electrochemical behavior preferably, particularly the prepared Co of embodiment 3 3O 4Capability retention behind material charge and discharge cycles 40 circles has embodied best electrochemical stability and cycle life more than 97%.
Foregoing is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (8)

1. Co 3O 4The flower-shaped preparation methods of microballoon is characterized in that this method comprises following concrete steps:
(1), with stir after cobalt salt, tensio-active agent, precipitation agent and the solvent 30
Figure 2011103197126100001DEST_PATH_IMAGE001
60min; Carry out hydro-thermal reaction in the autoclave with whole mixing solutions immigration inner liner polytetrafluoroethylene; The control hydrothermal temperature be 95
Figure 709316DEST_PATH_IMAGE001
105 ℃; Time be 3.5
Figure 523689DEST_PATH_IMAGE001
4.5h, reaction solution;
Wherein said cobalt salt is Xiao Suangu, cobaltous acetate, cobaltous carbonate or cobalt oxalate;
Said tensio-active agent is the cetyl trimethyl ammonia bromide;
Described precipitation agent is a urea;
Described solvent is water, Pentyl alcohol and hexanaphthene; Wherein the ratio of mixture of solvent is calculated by volume, i.e. water: Pentyl alcohol: hexanaphthene be 18
Figure 346151DEST_PATH_IMAGE001
31.3:1:20;
Wherein the ratio of mixture of cobalt salt, tensio-active agent, precipitation agent and solvent is calculated in molar ratio, i.e. cobalt salt: tensio-active agent: precipitation agent: the water in the solvent is 1.82:1:7.27:545.45
Figure 550868DEST_PATH_IMAGE001
949.09;
(2), washing and oven dry obtain the powder-mixed presoma;
Carry out the reaction solution of step (1) gained centrifugal; Centrifugal process control centrifugal rotational speed be 3000
Figure 749768DEST_PATH_IMAGE001
3500r/min; Time be 20
Figure 356330DEST_PATH_IMAGE001
30min; Oven dry after solid substance behind gained centrifugal respectively washs 3 times with deionized water and absolute ethyl alcohol, the powder-mixed presoma;
The deionized water that wherein each washing is used and the amount of absolute ethyl alcohol are by reaction solution: the volume ratio of deionized water is 1:50, and by reaction solution: the volume ratio of absolute ethyl alcohol is 1:1.5;
Wherein bake out temperature be controlled to be 60
Figure 349693DEST_PATH_IMAGE001
90 ℃;
(3), with the thermal treatment under air atmosphere of powder-mixed presoma, Co 3O 4The flower-shaped material of microballoon
Is 290 with the powder-mixed presoma of step (2) gained in temperature
Figure 104023DEST_PATH_IMAGE001
Thermal treatment 3h under 310 ℃ of conditions promptly gets a kind of Co 3O 4The flower-shaped material of microballoon.
2. a kind of Co as claimed in claim 1 3O 4The flower-shaped preparation methods of microballoon, it is characterized in that the ratio of mixture of the solvent in the step (1) is calculated by volume, i.e. water: Pentyl alcohol: hexanaphthene is preferably 28:1:20.
3. a kind of Co as claimed in claim 2 3O 4The flower-shaped preparation methods of microballoon; The ratio of mixture that it is characterized in that cobalt salt, tensio-active agent, precipitation agent and solvent in the step (1) is calculated in molar ratio, i.e. cobalt salt: tensio-active agent: precipitation agent: the water in the solvent is preferably 1.82:1:7.27:848.48.
4. like claim 1,2 or 3 described a kind of Co 3O 4The flower-shaped preparation methods of microballoon is characterized in that:
The filling degree of step (1) mesohigh reaction kettle be 60
Figure 841035DEST_PATH_IMAGE001
80%; Hydrothermal temperature is preferably 100 ℃, and the hydro-thermal reaction time is preferably 4h;
Bake out temperature control in the step (2) is preferably 80 ℃;
Thermal treatment temp in the step (3) is preferably 300 ℃.
5. a kind of Co as claimed in claim 4 3O 4The flower-shaped preparation methods of microballoon is characterized in that the filling degree of the autoclave in the step (1) is preferably 75%.
6. a kind of Co as claimed in claim 4 3O 4A kind of Co of the flower-shaped preparation methods gained of microballoon 3O 4The flower-shaped material of microballoon is characterized in that the flower-shaped scantling of this microballoon is 2
Figure 302103DEST_PATH_IMAGE001
5
Figure 2011103197126100001DEST_PATH_IMAGE002
M.
7. like claim 1,2 or 3 described a kind of Co 3O 4A kind of Co of the flower-shaped preparation methods gained of microballoon 3O 4The flower-shaped material of microballoon is characterized in that a kind of Co of gained 3O 4The negative material that the flower-shaped material of microballoon is used for chargeable lithium ion battery is a tricobalt tetroxide electrode negative material.
8. a kind of Co as claimed in claim 7 3O 4The negative material that the nano-sheet material is used for chargeable lithium ion battery is the preparation method of tricobalt tetroxide electrode negative material, it is characterized in that step is following:
Pressing mass ratio to cobaltosic oxide nano flaky material, acetylene black and sticker calculates; Be the cobaltosic oxide nano flaky material: acetylene black: sticker is 80:15:5; Nano-sheet material, acetylene black and sticker are mixed and be dissolved in the N-Methyl pyrrolidone; Be coated on the nickel screen collector of handling,, promptly get tricobalt tetroxide electrode negative material in 100 ℃ in vacuum, baking 12h;
Described sticker is a PVDF.
CN2011103197126A 2011-10-20 2011-10-20 Co3O4 microsphere flower-like material as well as preparation method and application thereof Pending CN102502889A (en)

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CN107082455A (en) * 2017-04-25 2017-08-22 西北师范大学 A kind of nickel doped cobaltic-cobaltous oxide nano flower and preparation method thereof
CN107176620A (en) * 2017-04-05 2017-09-19 郑州轻工业学院 A kind of method for preparing different morphologies transition metal oxide electrode material
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CN112635755A (en) * 2020-12-22 2021-04-09 江西理工大学 In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere
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CN102849804A (en) * 2012-09-21 2013-01-02 中国科学院过程工程研究所 Cobaltosic oxide columnar structure material and preparation method thereof
CN102849804B (en) * 2012-09-21 2014-11-05 中国科学院过程工程研究所 Cobaltosic oxide columnar structure material and preparation method thereof
CN102923791A (en) * 2012-10-29 2013-02-13 江苏大学 Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method
CN102923791B (en) * 2012-10-29 2014-07-30 江苏大学 Method for preparing multi-tunnel cobaltosic oxide flower-like microspheres by solvothermal method
CN103771544A (en) * 2014-02-22 2014-05-07 吉林大学 Preparation method of hollow cobaltosic oxide microsphere
CN103771544B (en) * 2014-02-22 2015-04-22 吉林大学 Preparation method of hollow cobaltosic oxide microsphere
CN104085858A (en) * 2014-06-27 2014-10-08 江苏华东锂电技术研究院有限公司 Preparation method of metal oxide
CN105870439A (en) * 2016-04-22 2016-08-17 济南大学 Preparation method and application of porous Co3O4
CN105870439B (en) * 2016-04-22 2018-03-16 济南大学 A kind of preparation method and applications of porous cobaltosic oxide
CN106180748A (en) * 2016-07-15 2016-12-07 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method carrying silver porous cobaltosic oxide nano composite material
CN107176620A (en) * 2017-04-05 2017-09-19 郑州轻工业学院 A kind of method for preparing different morphologies transition metal oxide electrode material
CN107082455A (en) * 2017-04-25 2017-08-22 西北师范大学 A kind of nickel doped cobaltic-cobaltous oxide nano flower and preparation method thereof
CN107082455B (en) * 2017-04-25 2018-10-26 西北师范大学 A kind of nickel doped cobaltic-cobaltous oxide nano flower and preparation method thereof
CN107381660A (en) * 2017-08-02 2017-11-24 上海纳米技术及应用国家工程研究中心有限公司 Sb, Mn codope cobaltosic oxide nano flower-like microsphere preparation method
CN109346721A (en) * 2018-09-30 2019-02-15 上海应用技术大学 NiCo2O4Material and its preparation and application
CN110416509A (en) * 2019-07-17 2019-11-05 肇庆市华师大光电产业研究院 A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof
CN110416509B (en) * 2019-07-17 2021-05-25 肇庆市华师大光电产业研究院 High-specific-capacity lithium ion battery negative electrode material and preparation method thereof
CN111056574A (en) * 2019-12-31 2020-04-24 华北水利水电大学 Method for preparing pattern Co on foam nickel substrate3O4Method for preparing nano material
CN113371764A (en) * 2020-03-10 2021-09-10 荆门市格林美新材料有限公司 Preparation method of flower-rod-shaped cobalt carbonate
CN113371764B (en) * 2020-03-10 2023-11-07 荆门市格林美新材料有限公司 Preparation method of flower-rod-shaped cobalt carbonate
CN112635755A (en) * 2020-12-22 2021-04-09 江西理工大学 In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere
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