CN109616644A - Silk gum carbon film coated Co3O4Porous microsphere composite material and preparation method - Google Patents
Silk gum carbon film coated Co3O4Porous microsphere composite material and preparation method Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of silk gum carbon film coated Co3O4Porous microsphere composite material and preparation method.The present invention is by by Co3O4Porous microsphere is soaked in silk gum solution, then centrifugation, drying carry out high temperature sintering, obtain with silk gum carbon film coated Co3O4Porous microsphere composite material.The method of the present invention preparation cost is cheap, simple process, and low-carbon environment-friendly, obtained silk gum carbon film coated Co3O4Porous microsphere conductivity of composite material is good, and cyclical stability is high, can be used as the positive electrode of lithium-sulfur cell.
Description
Technical field
The invention belongs to the technical fields of battery material, more particularly to a kind of silk gum carbon film coated Co3O4Porous microsphere is multiple
Condensation material and preparation method thereof.
Background technique
Cobaltosic oxide (Co3O4) it is a kind of typical transition metal oxide, crystal structure is typical spinelle knot
Structure, wherein O2-For cubic close accumulation, Co2+Ion is four-coordination, is filled in oxygen tetrahedron gap, and Co3+Ion is matched for six
Position, is filled in oxygen octahedra gap.Co3O4Unique crystal structure, excellent mechanical stability and good chemical property make
It has in new energy fields such as supercapacitor, lithium ion battery, lithium-sulfur cells compares broad application prospect.
Currently, as battery electrode material, Co3O4Have become most fast one of the transition metal oxide of research and development, reason
It is Co3O4With following tempting unique advantage: a) raw material is easy to get, and synthesis is simple；B) there is superelevation as lithium cell negative pole material
Theoretical capacity, about 890mAh g-1；C) it is prepared with good environmental stability, such as Wang X et al. hydro-thermal method
Co3O4Hollow ball is applied to lithium ion battery negative material (Synthesis and Lithium Storage Properties
of Co3O4Nanosheet-Assembled Multishelled Hollow Spheres.Advanced Functional
2010), under 0.2C multiplying power, first discharge specific capacity reaches 1192.3mAh/ to Materials, Vol.20, No.10, May 25
G, specific capacity is maintained at 544mAh/g after 170 circles, and single cycle capacitance loss rate is about 0.2%.
However the positive electrode as lithium-sulfur cell, single Co3O4Electrochemical performance it is unsatisfactory.The main reason is that
Active material cannot all activate participation discharge and recharge reaction, in addition Co3O4Electric conductivity is bad, sulphur volume expansion in charge and discharge process
The problems such as serious, to limit it in the development of energy storage field.For these problems, people have done a large amount of improvements,
In one of relatively effective method be exactly in Co3O4Middle incorporation carbon material, carbon material not only good cycling stability, but also have mostly
There is good electric conductivity, so in Co3O4In by mixing a small amount of carbon material, be to improve its electric conductivity to improve battery electrification
Learn one of the effective way of performance.
Summary of the invention
The purpose of the present invention is to provide a kind of silk gum carbon film coated Co3O4Porous microsphere composite material and preparation method.
Co in the present invention3O4Porous microsphere can accommodate volume change of the sulphur in charge and discharge process, and it is slow to adsorb polysulfide
Solve shuttle effect.Meanwhile the carbon film of external sheath can play the role of improving sulphur positive conductive, thus to improve lithium sulphur electricity
Pond entirety chemical property provides a kind of resolving ideas.In addition, preparation method simple process of the invention, environmentally protective.
To achieve the above object, the present invention takes following technical scheme:
A kind of silk gum carbon film coated Co3O4The preparation method of porous microsphere composite material, comprising the following steps:
(1) Co is prepared using solvent-thermal method3O4Porous microsphere；
(2) Co for obtaining step (1)3O4Porous microsphere is soaked in silk gum aqueous solution, and after impregnating sufficiently, centrifugation is done
It is dry；
(3) powder of step (2) after dry is placed in tube furnace, under inert gas protection, is calcined at 400-700 DEG C
2-6h obtains silk gum carbon film coated Co3O4The composite material of porous microsphere.
Further, in the above-mentioned methods, step (1) prepares Co using solvent-thermal method3O4The specific steps of porous microsphere are such as
Under:
(1.1) four acetate hydrate cobalt (Co (CH are taken3COO)2·4H2O), it is dissolved in the ethylene glycol ((CH of certain volume2OH)2),
It is stirred at room temperature uniformly, a certain amount of polyvinylpyrrolidone (PVP) is then added, continues to be uniformly mixed, as network
Close cobalt salt solution；
(1.2) the complexing cobalt salt solution that step (1.1) obtains is transferred in the polytetrafluoroethyllining lining of autoclave,
10-16h is reacted at 160-200 DEG C, obtained solution dehydrated alcohol centrifugal elutriation to solution is clarified, is done at 60-100 DEG C
Dry 12h, obtains precursor powder；
(1.3) precursor powder prepared by step (1.2) is placed in sintering furnace and calcines 2-4h, calcination temperature is in 400-
600 DEG C, obtain Co3O4Porous microsphere.
Further, in the above-mentioned methods, the mass ratio of the four acetate hydrates cobalt and polyvinylpyrrolidone is 1:
0.01-0.08, the solution concentration that four acetate hydrate cobalts are dissolved in ethylene glycol formation is 50-160mmol/L.
Further, in the above-mentioned methods, the polyvinylpyrrolidone is PVP-K30, and average relative molecular mass is
40000。
Further, in the above-mentioned methods, the silk gum concentration of aqueous solution of the step (2) is 0.5-2mmol/L.
Further, in the above-mentioned methods, the silk gum molecular weight in the step (2) is 5000-10000.
Further, in the above-mentioned methods, the soaking time of the step (2) is 0.5-1h.
The present invention also provides a kind of silk gum carbon film coated Co prepared by the above method3O4Porous microsphere composite material.
Further, in the above-mentioned methods, the silk gum carbon film coated Co3O4The diameter of porous microsphere composite material is
1.5-2μm。
The present invention also provides above-mentioned silk gum carbon film coated Co3O4Application of the porous microsphere composite material in electrode material.
The present invention has following technical characterstic:
1) present invention makees carbon source not only low-carbon environment-friendly, but also waste utilization using organic sericin, can further decrease
Cost of manufacture.
2) silk gum carbon film coated Co prepared by the present invention3O4Porous microsphere composite material is used as lithium sulfur battery anode material, energy
Effectively alleviate the volume expansion of sulphur in lithium-sulfur cell charge and discharge process, Co3O4Porous microsphere is to polysulfide dissolved with certain
Obtain inhibiting effect；The cladding of silk gum carbon film effectively improves the electric conductivity of sulphur positive electrode simultaneously, improves lithium-sulfur cell
Cyclical stability.
Detailed description of the invention
Fig. 1 is the silk gum carbon film coated Co prepared in embodiment 13O4The SEM of porous microsphere schemes.
Fig. 2 is that S@Co is made in embodiment 13O4/ C is the lithium-sulfur cell of positive electrode with 1C charge and discharge 200 times cyclicity
It can figure.
Specific embodiment
Following specific embodiments are the further explanations to method provided by the invention and technical solution, but are not construed as
Limitation of the present invention.
In the specific embodiment of the invention, silk gum carbon film coated Co3O4Porous microsphere composite material is applied to lithium-sulfur cell
In, specific test process is as follows: in the glove box of argon gas protection, the S@C/Co of preparation3O4For anode, Celgard 2500 makees
For diaphragm, metal lithium sheet is as cathode, the LiNO of LiTFSI (DOL/DME=1:1) the addition 0.1mol/L of 1.0mol/L3As
Electrolyte assembled battery.In charging-discharge tester system, charge-discharge test voltage is 1.5-3.0V.
Embodiment 1
The four acetate hydrate cobalts of 0.015mol are dissolved in 30ml ethylene glycol, magnetic agitation forms homogeneous solution at room temperature,
The polyvinylpyrrolidone for adding 0.0225g continues after stirring 0.5h, is put into the polytetrafluoroethyllining lining of autoclave
In, 12h is reacted at 180 DEG C, acquired solution dehydrated alcohol is rinsed three times, centrifuge separation, isolated sediment exists
Dry 12h at 70 DEG C.
Presoma after drying is moved into sintering furnace, 3 DEG C of heating rate, 500 DEG C of sintering temperature, calcines 3h, obtain
Co3O4Porous microsphere.Again by Co3O4Porous microsphere powder is immersed in silk gum (molecular weight 8000) aqueous solution of 2mmol/L
1h is centrifuged later, and the sediment isolated is dried 12h at 80 DEG C.Powder after drying is placed in tube furnace
3h is calcined under nitrogen protection atmosphere, calcination temperature obtains silk gum carbon film coated Co at 600 DEG C3O4The composite wood of porous microsphere
Material.
The sublimed sulfur of 49mg is dissolved in CS2In solution, the silk gum carbon film coated Co of 21mg is added3O4Porous microsphere powder, room
Temperature is lower to be stirred to drying.Mixture is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, 155 DEG C of heat preservations again
12 hours, obtain S@C/Co3O4Compound.
By S@Co3O4/ C composite, Ketjen black, PVDF are uniformly mixed according to mass ratio 7:2:1, N-Methyl pyrrolidone
Concentration is adjusted, stirring 3h makes slurry.The slurry made knife coating is applied on a current collector, the lower 60 DEG C of bakings of vacuum environment
Dry 12h.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Fig. 1 is the silk gum carbon film coated Co prepared in the present embodiment3O4The SEM of porous microsphere schemes, it can be seen that Co3O4It is more
The diameter of hole microballoon is about 1.8 μm.Fig. 2 is S@C/Co obtained in the present embodiment3O4It is filled for the lithium-sulfur cell of positive electrode with 1C
The charging and discharging capacity and coulombic efficiency curve that electric discharge is 200 times.
Electrochemical property test is the result shows that the S@C/Co prepared in this example3O4Composite material is put for the first time under 1C multiplying power
Electric specific capacity reaches 876.8mAh/g, and 314.3mAh/g is still possessed after circulation 200 times, and 50 enclose single cycle capacitance loss later
Rate is about 0.12%, and average coulombic efficiency is maintained at 99.74%.
Comparative example 1
The four acetate hydrate cobalts of 0.015mol are dissolved in 30ml ethylene glycol, magnetic agitation forms homogeneous solution at room temperature,
The polyvinylpyrrolidone for adding 0.0225g continues after stirring 1h, is put into the polytetrafluoroethyllining lining of autoclave,
12h is reacted at 180 DEG C, acquired solution dehydrated alcohol is rinsed three times, centrifuge separation, isolated sediment is at 70 DEG C
Lower dry 12h.Presoma after drying is moved into sintering furnace, 3 DEG C of heating rate, 500 DEG C of sintering temperature, calcines 3h, obtain
Co3O4Porous microsphere.
The sublimed sulfur of 49mg is dissolved in CS2In solution, the Co of 21mg is added3O4Porous microsphere powder is stirred at room temperature to dry
It is dry.Mixture is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection again, 155 DEG C of heat preservation 12h obtain S@
Co3O4Compound.
By S@Co3O4Composite material, Ketjen black, PVDF are uniformly mixed according to mass ratio 7:2:1, N-Methyl pyrrolidone tune
Concentration is saved, stirring 3h makes slurry.The slurry made knife coating is applied on a current collector, the lower 60 DEG C of drying of vacuum environment
12h.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
The S@Co prepared in this comparative example3O4Composite material is not directly used as electrode material by sericin cladding,
Electrochemical property test is the result shows that first discharge specific capacity only reaches 457.3mAh/g under 1C multiplying power, after recycling 200 times only
Surplus 187.3mAh/g, single cycle capacitance loss rate is about 0.28%, and average coulombic efficiency is maintained at 98.62%, the electricity of battery
Chemical manifestations are integrally all weaker than embodiment 1.
Comparative example 2
The four acetate hydrate cobalts of 0.015mol are dissolved in 30ml ethylene glycol, magnetic agitation forms homogeneous solution at room temperature,
The polyvinylpyrrolidone for adding 0.01875g continues after stirring 0.5h, is put into the polytetrafluoroethyllining lining of autoclave
In, 10h is reacted at 160 DEG C, acquired solution dehydrated alcohol is rinsed three times, centrifuge separation, isolated sediment exists
Dry 12h at 70 DEG C.
Presoma after drying is moved into sintering furnace, 3 DEG C of heating rate, 500 DEG C of sintering temperature, calcines 3h, obtain
Co3O4Porous microsphere.Again by Co3O4Porous microsphere powder is immersed in silk gum (molecular weight 8000) aqueous solution of 0.5mmol/L
1h is centrifuged later, and the sediment isolated is dried 12h at 80 DEG C.Powder after drying is placed in tube furnace
2h is calcined under nitrogen protection atmosphere, calcination temperature obtains silk gum carbon film coated Co at 500 DEG C3O4The composite wood of porous microsphere
Material.
The sublimed sulfur of 49mg is dissolved in CS2In solution, the silk gum carbon film coated Co of 21mg is added3O4Porous microsphere powder, room
Temperature is lower to be stirred to drying.Mixture is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, 155 DEG C of heat preservations again
12h obtains S@C/Co3O4Compound.
By S@C/Co3O4Composite material, Ketjen black, PVDF are uniformly mixed according to mass ratio 7:2:1, N-Methyl pyrrolidone
Concentration is adjusted, stirring 3h makes slurry.The slurry made knife coating is applied on a current collector, the lower 60 DEG C of bakings of vacuum environment
Dry 12h.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Electrochemical property test is the result shows that the S@C/Co prepared in this comparative example3O4Composite material under 1C multiplying power for the first time
Specific discharge capacity reaches 820.7mAh/g, and 282.4mAh/g is still possessed after circulation 200 times, and 50 enclose single cycle capacity damage later
Mistake rate is about 0.192%, and average coulombic efficiency substantially remains in 99.54%, and the electrochemical performance of battery is integrally slightly weaker than implementation
Example 1.
Comparative example 3
The four acetate hydrate cobalts of 0.015mol are dissolved in 40ml ethylene glycol, magnetic agitation forms homogeneous solution at room temperature,
The polyvinylpyrrolidone for adding 0.03g continues after stirring 1h, is put into the polytetrafluoroethyllining lining of autoclave, in
16h is reacted at 200 DEG C, acquired solution dehydrated alcohol is rinsed three times, centrifuge separation, isolated sediment is at 70 DEG C
Dry 12h.
Presoma after drying is moved into sintering furnace, 3 DEG C of heating rate, 700 DEG C of sintering temperature, calcines 4h, obtain
Co3O4Porous microsphere.Again by Co3O4Porous microsphere powder is immersed in silk gum (molecular weight 5000) aqueous solution of 2mmol/L
1h is centrifuged later, and the sediment isolated is dried 12h at 80 DEG C.Powder after drying is placed in tube furnace
6h is calcined under nitrogen protection atmosphere, calcination temperature obtains silk gum carbon film coated Co at 600 DEG C3O4The composite wood of porous microsphere
Material.
The sublimed sulfur of 49mg is dissolved in CS2In solution, the silk gum carbon film coated Co of 21mg is added3O4Porous microsphere powder, room
Temperature is lower to be stirred to drying.Mixture is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, 155 DEG C of heat preservations again
16h obtains S@C/Co3O4Compound.
By S@C/Co3O4Composite material, Ketjen black, PVDF are uniformly mixed according to mass ratio 7:2:1, N-Methyl pyrrolidone
Concentration is adjusted, stirring 3h makes slurry.The slurry made knife coating is applied on a current collector, the lower 60 DEG C of bakings of vacuum environment
Dry 12h.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Electrochemical property test is the result shows that the S@C/Co prepared in this comparative example3O4Composite material under 1C multiplying power for the first time
Specific discharge capacity reaches 802.3mAh/g, and 272.6mAh/g is still possessed after circulation 200 times, and 50 enclose single cycle capacity damage later
Mistake rate is about 0.244%, and average coulombic efficiency is maintained at 98.44%, and the electrochemical performance of battery is integrally slightly weaker than embodiment 1.
Comparative example 4
The four acetate hydrate cobalts of 0.015mol are dissolved in 40ml ethylene glycol, magnetic agitation forms homogeneous solution at room temperature,
The polyvinylpyrrolidone for adding 0.02g continues after stirring 1h, is put into the polytetrafluoroethyllining lining of autoclave, in
14h is reacted at 170 DEG C, acquired solution dehydrated alcohol is rinsed three times, centrifuge separation, isolated sediment is at 70 DEG C
Dry 12h.
Presoma after drying is moved into sintering furnace, 3 DEG C of heating rate, 600 DEG C of sintering temperature, calcines 4h, obtain
Co3O4Porous microsphere.Again by Co3O4Porous microsphere powder is immersed in silk gum (molecular weight 8000) aqueous solution of 2mmol/L
1h is centrifuged later, and the sediment isolated is dried 12h at 80 DEG C.Powder after drying is placed in tube furnace
4h is calcined under nitrogen protection atmosphere, calcination temperature obtains silk gum carbon film coated Co at 600 DEG C3O4The composite wood of porous microsphere
Material.
The sublimed sulfur of 49mg is dissolved in CS2In solution, the silk gum carbon film coated Co of 21mg is added3O4Porous microsphere powder, room
Temperature is lower to be stirred to drying.Mixture is moved into the polytetrafluoroethylene (PTFE) stainless steel cauldron under argon atmosphere protection, 155 DEG C of heat preservations again
14h obtains S@C/Co3O4Compound.
By S@C/Co3O4Composite material, Ketjen black, PVDF are uniformly mixed according to mass ratio 7:2:1, N-Methyl pyrrolidone
Concentration is adjusted, stirring 3h makes slurry.The slurry made knife coating is applied on a current collector, the lower 60 DEG C of bakings of vacuum environment
Dry 12h.It is cut into the round pole piece that diameter is 16mm and assembled battery test.
Electrochemical property test is the result shows that the S@C/Co prepared in this comparative example3O4Composite material under 1C multiplying power for the first time
Specific discharge capacity reaches 842.3mAh/g, and 302.6mAh/g is still possessed after circulation 200 times, and 50 enclose single cycle capacity damage later
Mistake rate is about 0.244%, and average coulombic efficiency is maintained at 99.44%, is influenced by silk gum concentration, causes the performance of battery slightly lower
In embodiment 1.
The method of the present invention that the above embodiments are only used to help understand and its core concept.It should be pointed out that for
For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention
Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection scope.
Claims (10)
1. a kind of silk gum carbon film coated Co3O4The preparation method of porous microsphere composite material, which comprises the following steps:
(1) Co is prepared using solvent-thermal method3O4Porous microsphere；
(2) Co for obtaining step (1)3O4Porous microsphere is soaked in silk gum aqueous solution, after impregnating sufficiently, centrifugation, drying；
(3) powder of step (2) after dry is placed in tube furnace, under inert gas protection, in 400-700 DEG C of calcining 2-
6h obtains silk gum carbon film coated Co3O4The composite material of porous microsphere.
2. preparation method according to claim 1, which is characterized in that the step (1) prepares Co using solvent-thermal method3O4
Specific step is as follows for porous microsphere:
(1.1) four acetate hydrate cobalt (Co (CH are taken3COO)2·4H2O), it is dissolved in the ethylene glycol ((CH of certain volume2OH)2), in room
It is stirred evenly under temperature, a certain amount of polyvinylpyrrolidone (PVP) is then added, continues to be uniformly mixed, as complex cobalt
Salting liquid；
(1.2) the complexing cobalt salt solution that step (1.1) obtains is transferred in the polytetrafluoroethyllining lining of autoclave, in
10-16h is reacted at 160-200 DEG C, obtained solution dehydrated alcohol centrifugal elutriation to solution is clarified, it is dry at 60-100 DEG C
12h obtains precursor powder；
(1.3) precursor powder prepared by step (1.2) is placed in sintering furnace and calcines 2-4h, calcination temperature at 400-600 DEG C,
Obtain Co3O4Porous microsphere.
3. preparation method according to claim 2, which is characterized in that the four acetate hydrates cobalt and polyvinylpyrrolidone
Mass ratio be 1:0.01-0.08, four acetate hydrate cobalts be dissolved in ethylene glycol formation solution concentration be 50-160mmol/L.
4. preparation method according to claim 2, which is characterized in that the polyvinylpyrrolidone is PVP-K30, average
Relative molecular weight is 40000.
5. preparation method according to claim 1, which is characterized in that the silk gum concentration of aqueous solution of the step (2) is
0.5-2mmol/L。
6. preparation method according to claim 1, which is characterized in that the silk gum molecular weight in the step (2) is 5000-
10000。
7. preparation method according to claim 1, which is characterized in that the soaking time of the step (2) is 0.5-1h.
8. a kind of silk gum carbon film coated Co being prepared by the described in any item preparation methods of claim 1-73O4Porous microsphere
Composite material.
9. composite material according to claim 8, which is characterized in that the silk gum carbon film coated Co3O4Porous microsphere is compound
The diameter of material is 1.5-2 μm.
10. a kind of such as the described in any item silk gum carbon film coated Co of claim 1-93O4Porous microsphere composite material is in electrode material
Application in material.
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| CN111244424A (en) * | 2020-01-19 | 2020-06-05 | 杭州电子科技大学 | Preparation method of sericin carbon film coated Ni/NiO microsphere composite material |
| CN111244424B (en) * | 2020-01-19 | 2020-12-22 | 杭州电子科技大学 | Preparation method of sericin carbon film coated Ni/NiO microsphere composite material |
| CN111740083A (en) * | 2020-06-12 | 2020-10-02 | 新昌县华发机械股份有限公司 | Carbon-coated porous Co3O4Microsphere lithium ion battery cathode material and preparation method thereof |
| CN113161762A (en) * | 2021-04-15 | 2021-07-23 | 浙江理工大学 | Core-shell structure metal/sericin-based carbon nano composite wave-absorbing material and preparation method thereof |
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Application publication date: 20190412 |