CN104953114B - Cobaltosic oxide-stannic disulfide nano-complex preparation method - Google Patents
Cobaltosic oxide-stannic disulfide nano-complex preparation method Download PDFInfo
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- CN104953114B CN104953114B CN201510228161.0A CN201510228161A CN104953114B CN 104953114 B CN104953114 B CN 104953114B CN 201510228161 A CN201510228161 A CN 201510228161A CN 104953114 B CN104953114 B CN 104953114B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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 discloses a kind of preparation method of cobaltosic oxide-stannic disulfide nano-complex, hydro-thermal method is used to prepare silk ball shape stannic disulfide as presoma, it is mixed with cobalt acetate and cobalt potassium cyanate, the compound of stannic disulfide and cobalt cyanic acid cobalt is generated by temperature constant magnetic stirring, then high annealing is carried out, the cobaltosic oxide uniformly compound stannic disulfide composite material with surface inside it is made.The present invention is environment friendly and pollution-free, and at low cost, preparation process is simple, and modified stannic disulfide composite material obtained has higher capacity and better cyclical stability compared with stannic disulfide monomer.
Description
Technical field
The present invention relates to the negative electrode material of a kind of lithium ion battery negative material more particularly to a kind of curing tinbase and its
Preparation method.
Background technique
Currently, since fossil fuels are increasingly depleted, energy crisis is more serious, at the same environmental degradation aggravate, green and can
The renewable sources of energy become every country and fall over each other the target pursued.In order to make full use of renewable energy, cheap stable power storage
System will be crucial.Lithium ion battery is since with high-energy, long-life, low consumption, nuisanceless and self discharge be small, internal resistance
Small, the advantages that cost performance is high, pollution is few, it is widely used in the fields such as photoelectricity, information, traffic, defense military.As people offset
Expense electronic product requires the development of the vehicles such as higher and higher and electric car, need of the people to high performance lithium ion battery
Ask more more and more urgent, conventional lithium ion battery can no longer meet the demand of high capacity power battery.Therefore, develop high capacity,
Long-life, stabilization, safe, inexpensive new type lithium ion battery are of great significance.
The building block of lithium ion battery includes anode, cathode and electrolyte, and negative electrode material is to the comprehensive of lithium ion battery
Performance, including energy density, power density and cycle life etc. are closed, there is great influence.In business lithium battery, mostly
Use the graphite with good circulation performance as negative electrode material, still, the theoretical capacity of graphite is only 372mAh/g, is limited
The application range of lithium ion battery.Therefore, it will greatly be pushed away using the new electrode material nanostructure of new electrode material and design
The development of dynamic lithium ion battery.
With commercialized carbon material graphite-phase ratio, stannic disulfide has higher volume and specific discharge capacity.But it is filling
The enormousness variation of stannic disulfide will lead to the dusting of electrode in discharge process, so that capacity sharp-decay.Pass through structure
Specific nanostructure and composite material are built, the disadvantage that capacity attenuation can not only be overcome fast, moreover it is possible to largely improve it
Cycle life.
Chinese document " lithium ion battery kamash alloy and its cathode composite progress " (Science&
2007 Vol.25 No.22 of Technology Review) it proposes to use carbon coating kamash alloy material.Although composite material
Electric conductivity gets a promotion, but the capacity attenuation of tin-based material itself is not improved.
A kind of tin-cobalt alloy negative pole material of lithium-ion battery as disclosed in Chinese patent application discloses No. 101924203A
Preparation method use electrodeposition process plating tin-cobalt alloy on it using nickel seine as substrate to form alloy firm layer；Tin cobalt
Electric depositing solution group becomes, 30~60g/L of soluble cobalt；Soluble 20~60g/L of pink salt；K4P2O7200~400g/L；Sulphur
Urea: 5~10g/L；PH:8~10.However, the tin-cobalt alloy negative pole material of lithium-ion battery of this method preparation is not from substantially/object
Manage the capacity fade problem for improving tin-based material itself in characteristic.
For another example Chinese patent application discloses a kind of lithium ion battery artificial gold/rare earth gold of No. 103094562A announcement
The preparation method for belonging to negative electrode material, obtains SnS using hydro-thermal method2/ rare earth metal (Ce, La, Nd etc.) material, the rare earth of synthesis
The SnS of metal (Ce, La, Nd etc.) doping2Material, due to the doping of rare earth metal (Ce, La, Nd etc.), large-sized rare earth gold
Belong to (Ce, La, Nd etc.) ionic compartmentation Sn ion and enters SnS2In lattice, big lattice structure can provide for the deintercalation of lithium ion
Bigger lattice vacancy, so that capacity and cycle performance are improved, so that SnS2/ rare earth metal (Ce, La, Nd etc.) negative electrode material
Capacity is higher than pure phase SnS2Cycle performance.However, lithium ion battery artificial gold/rare earth metal cathode material of this method preparation
Material does not also improve the capacity fade problem of tin-based material itself from substantially/physical characteristic.
For another example Chinese patent application discloses a kind of spherical artificial gold of nano bar-shape composition of No. 103915625A announcement
Preparation method and application after mixing by sulphur source and tin source and surfactant heat mixed solution using hydro-thermal method,
The lithium cell negative pole material for the spherical artificial gold being made of nano bar-shape is obtained after the product that filtration drying obtains.However, although should
Method is prepared for spherical artificial gold, but its capacity attenuation for not improving tin-based material itself from substantially/physical characteristic yet is asked
Topic.
Therefore it provides a kind of-two sulphur of cobaltosic oxide for the capacity fade problem that can sufficiently improve tin-based material itself
Changing tin nano-complex and preparation method thereof becomes urgent problem in the industry.
Summary of the invention
The object of the present invention is to provide a kind of cobaltosic oxide-stannic disulfide nano-complex and preparation method thereof, the party
The capacity of the easy environmental protection of method, the modified stannic disulfide compound of gained is big, and cyclical stability is high.
According to an aspect of the present invention, a kind of cobaltosic oxide-stannic disulfide nano-complex is provided, comprising: mole
Than the cobaltosic oxide and stannic disulfide for 1:2~1:5, wherein stannic disulfide is silk ball shape stannic disulfide, cobaltosic oxide
Grain dispersion is incorporated into the gap in the petal surface of silk ball shape stannic disulfide and between adjacent petal to silk ball shape curing
The petal of tin applies stress, so that the petal pattern of silk ball shape stannic disulfide changes to make silk ball shape stannic disulfide
Hole become smaller.
Preferably, which includes the cobaltosic oxide and two sulphur that molar ratio is 1:3~1:4 (such as 1:3.5 or so)
Change tin.
Preferably, 20%~40% (such as 30% or so) dispersion in cobaltosic oxide particle is incorporated into two sulphur of silk ball shape
In the petal surface for changing tin, 60%~80% (such as 70% or so) dispersion in cobaltosic oxide particle is incorporated into silk ball shape two
In gap between the adjacent petal of artificial gold, so that the petal pattern of silk ball shape stannic disulfide occurs to fold and/or crimp.
According to another aspect of the present invention, a kind of preparation side of cobaltosic oxide-stannic disulfide nano-complex is provided
Method comprising: (1), prepare silk ball shape stannic disulfide；(2), by ready silk ball shape stannic disulfide 1:100 in mass ratio~
1:500 is distributed in the cobalt cyanic acid potassium solution of 0.01~0.03 mol/L, is stirred 2~4 hours, is formed containing before stannic disulfide
Drive the suspension of body；(3), by the suspension containing stannic disulfide presoma prepared, 2:1~1:2 is added 0.01 by volume
It in the cobalt acetate solution of~0.03 mol/L, stirs 2~5 hours, forms the compound of stannic disulfide and cobalt cyanic acid cobalt；(4),
The compound of the stannic disulfide and cobalt cyanic acid cobalt that prepare after washing, is dried in vacuo 8~16 hours；And (5), will dry
The compound of stannic disulfide afterwards and cobalt cyanic acid cobalt is annealed under inert gas protection, and annealing temperature is 350~550 degrees Celsius,
Cobaltosic oxide-stannic disulfide nano-complex is made in annealing 1~3 hour.
Selectively, silk ball shape stannic disulfide can be obtained or by preparing by purchase.
Selectively, preparing silk ball shape stannic disulfide in step (1) includes: (1.1), in mass ratio 1:1:90~110
Five hydration artificial golds and thioacetamide are added in 99% volume ethanol solution, magnetic agitation acquisition in 2~4 hours clarification is molten
Liquid；(1.2), the clear solution obtained carries out vacuum hydro-thermal reaction, and hydrothermal temperature is 160~180 degrees Celsius, the reaction time
It is 12~14 hours, natural cooling after reaction；And 99% volume ethanol solution is successively used in (1.3), hydro-thermal reaction product
Being cleaned with deionized water to pH value is 5~7, is dried in vacuo 6~18 hours acquisition silk ball shape stannic disulfides.
Selectively, the washing times in step (1.3) can be 5~7 times.
Selectively, magnetic agitation, the matter of the suspension containing stannic disulfide presoma of acquisition are used in step (2)
Amount concentration is 1~2 mg/ml.
It selectively, can also be using other physical agitation modes come agitating solution in the present invention.
Selectively, magnetic stirring apparatus can be used to be stirred, utilizes the principle in magnetic field and whirlpool, when pedestal generates magnetic
After, stirrer is driven to move to achieve the purpose that stir liquid at circumferential cycle.
Selectively, temperature constant magnetic stirring is used in step (3), temperature is set as 25~30 degrees Celsius, and will contain
There is the suspension of stannic disulfide presoma by several times or is added dropwise in cobalt acetate solution.
Selectively, in step (4), two prepared are successively washed using 99% volume ethanol solution and deionized water
The compound of artificial gold and cobalt cyanic acid cobalt, and vacuum drying temperature is set as 50~60 degrees Celsius.
Selectively, cold after step (5) further comprises annealing the step of natural cooling under inert gas protection
But the time is 3~7 hours.
Selectively, inert gas is argon gas or xenon, and annealing can carry out in tube type resistance furnace, the liter in annealing process
Warm rate is set as 5~10 degrees celsius/minutes.
Selectively, hydro-thermal reaction can carry out in hydrothermal reaction kettle.
As a kind of alternative embodiment, a kind of preparation side of cobaltosic oxide-stannic disulfide nano-complex is provided
Method, comprising: prepare silk ball shape stannic disulfide；Prepare the bronzing suspension containing stannic disulfide presoma: by two above-mentioned sulphur
Change tin powder to be distributed in cobalt cyanic acid potassium solution, 2~3h of magnetic agitation forms stable bronzing suspension；The curing
It is 1~1.86mg/ml that tin, which disperses concentration of polymer solution,；Temperature constant magnetic stirring prepares the compound of stannic disulfide Yu cobalt cyanic acid cobalt:
Above-mentioned bronzing suspension is added dropwise in cobalt acetate solution, constant temperature stirs 3~4h, forms stannic disulfide and cobalt cyanic acid cobalt
Compound, and it is spare to wash vacuum drying；High annealing prepares the compound of stannic disulfide and cobaltosic oxide: will be above-mentioned compound
Object is placed in tube type resistance furnace, and the lower annealing of argon gas protection, heating rate is 6~10 DEG C/min, after cooling, collects powder, is made
The compound of stannic disulfide and cobaltosic oxide；The step of high annealing is as follows: annealing temperature is 450~550 DEG C, annealing
1~2h；Cooling procedure needs argon gas to protect simultaneously, and the rear 4~5h collects sample.Further, the silk ball shape curing
Tin preparation is as follows: five hydration artificial golds and thioacetamide 1:1 in mass ratio are added to the 99% volume ethanol solution of 150ml
In, after 2~3h of magnetic agitation, clear solution is moved into 200ml hydrothermal reaction kettle；Hydrothermal temperature is 160~180 DEG C,
Reaction time is 12~14h, after reaction natural cooling；Clean that (washing times are 5~7 with ethanol solution and deionized water
It is secondary) to pH value be 5~7, be dried in vacuo 6~18 hours.Preferably, cobalt potassium cyanate solution concentration is 0.02mol/L.Constant temperature stirring
Temperature is 25~30 DEG C.Vacuum drying temperature is 50~60 DEG C.Further, hydro-thermal reaction environment is heating in vacuum.
The beneficial effects of the present invention are: (1), according to the present invention, cobaltosic oxide is evenly embedded into the petal of stannic disulfide
Gap is distributed in petal surface, since stress causes petal pattern to occur to fold and crimp, becomes stannic disulfide hole
It is small, to be more advantageous to electrolyte storage and interionic exchange；(2), the present invention directly generates cobalt cyanic acid cobalt, phase using solwution method
Compound is prepared than usually used hydro-thermal method, the compound pattern that solwution method generates is controllable；(3), using hydro-thermal method
Stannic disulfide presoma is prepared, uses thioacetamide for Liu Yuan, raw material is cheap, and meets green chemical industry requirement；(4), it uses
Temperature constant magnetic stirring (solwution method) prepares compound, and preparation process is simple, and Material cladding is more abundant, abandons hydro-thermal method preparation,
Reducing uncertain factor influences；(5), cobaltosic oxide prepared by the present invention-stannic disulfide nano-complex first charge-discharge holds
Amount has large increase, and good cycling stability, and charge-discharge test is carried out under 100mA/g current density, measures and discharges for the first time
Capacity is 1343.1mAh/g, and initial charge capacity is 985.5mAh/g, after 50 circulations capacity be maintained at 778.0mAh/g with
On.
Detailed description of the invention
Fig. 1 is cobaltosic oxide of the invention-stannic disulfide nano-complex preparation flow schematic diagram.
Fig. 2 is the preparation flow schematic diagram of silk ball shape stannic disulfide of the invention.
Fig. 3 is the SEM figure of silk ball shape stannic disulfide prepared by the embodiment of the present invention 1.
Fig. 4 is the partial enlarged view of Fig. 3.
Fig. 5 is cobaltosic oxide-stannic disulfide nano-complex SEM figure prepared by the embodiment of the present invention 1.
Fig. 6 is the partial enlarged view of Fig. 5.
Fig. 7 is cobaltosic oxide-stannic disulfide nano-complex capacity-cycle-index prepared by the embodiment of the present invention 1
Curve graph.
Fig. 8 is the specific discharge capacity curve graph that the embodiment of the present invention 1 and comparative example 2 recycle 50 times.
Specific embodiment
Fig. 1 and Fig. 2 is please referred to, a kind of non-limiting embodiment according to the present invention provides a kind of cobaltosic oxide-
Stannic disulfide (Co3O4/SnS2) nano-complex preparation method, this approach includes the following steps.
Prepare silk ball shape stannic disulfide, which specifically includes: in mass ratio about 1:1:100 is hydrated artificial golds and sulphur for five
It is added in 99% volume ethanol solution for acetamide, about 4 hours acquisition clear solutions of magnetic agitation；The clear solution of acquisition into
Row vacuum hydro-thermal reaction, hydrothermal temperature are about 170 degrees Celsius, and the reaction time is about 13 hours, naturally cold after reaction
But；And it is about 6 that hydro-thermal reaction product, which is successively cleaned with 99% volume ethanol solution and deionized water to pH value, vacuum
Dry about 10 hours acquisition silk ball shape stannic disulfides.
The cobalt potassium cyanate that ready silk ball shape stannic disulfide in mass ratio about 1:300 is distributed to 0.015 mol/L is molten
In liquid, magnetic agitation about 2 hours, the suspension containing stannic disulfide presoma is formed.
By the vinegar of the suspension containing stannic disulfide presoma prepared 0.02 mol/L of about 1:1 addition by volume
In acidic cobalt solution, temperature constant magnetic stirring about 3 hours, the compound of stannic disulfide and cobalt cyanic acid cobalt is formed, wherein temperature is set as
About 27 degrees Celsius, and will be in the suspension containing stannic disulfide the presoma in ten times above addition cobalt acetate solution.
The stannic disulfide successively prepared using 99% volume ethanol solution and deionized water washing is answered with cobalt cyanic acid cobalt
After closing object, it is dried in vacuo about 10 hours, and vacuum drying temperature is set as about 55 degrees Celsius.
The compound of stannic disulfide and cobalt cyanic acid cobalt after drying is annealed under inert gas protection, annealing temperature is about
It 400 degrees Celsius, anneals about 2 hours, the heating rate in annealing process is set as 7 degrees celsius/minutes.Further, after annealing
Natural cooling under inert gas protection, cooling time are about 6 hours, and cobaltosic oxide-stannic disulfide nano-complex is made.
Referring to figure 5. and Fig. 6, cobaltosic oxide prepared in accordance with the present invention-stannic disulfide nano-complex include mole
Than the cobaltosic oxide and stannic disulfide for 1:3.5 or so.Stannic disulfide is silk ball shape stannic disulfide, in cobaltosic oxide particle
30% or so dispersion be incorporated into the petal surface of silk ball shape stannic disulfide, in cobaltosic oxide particle 70% or so dispersion
It is incorporated into the gap between the adjacent petal of silk ball shape stannic disulfide, flower of the cobaltosic oxide particle to silk ball shape stannic disulfide
The stress that valve applies makes the petal pattern of silk ball shape stannic disulfide occur to fold and/or crimp, to make silk ball shape two
The hole of artificial gold becomes smaller.
The present invention is made with comparative example combined with specific embodiments below and being further elaborated on, but embodiment and comparative example
It should not be construed as limiting the scope of the invention.
Embodiment 1
A kind of preparation method of cobaltosic oxide-stannic disulfide nano-complex, as shown in Figures 1 and 2, including following step
Rapid S1-S5.
In step sl, prepare silk ball shape stannic disulfide, specifically include step S11-S13.
In step s 11, by mass ratio be 1:1 five hydration artificial golds and thioacetamide respectively about 1.5g is added to about
In the 99% volume ethanol solution of 150ml, magnetic agitation 3h.
In step s 12, clear solution is moved into 200ml hydrothermal reaction kettle, it is anti-is put into progress hydro-thermal in vacuum oven
It answers, hydrothermal temperature is 160 DEG C, reaction time 12h, after reaction, natural cooling in case.
In step s 13, being cleaned respectively with 99% volume ethanol solution and deionized water to pH value is 7, is dried in vacuo 12h
It is spare.
Referring to figure 3. and Fig. 4, the SEM image of the silk ball shape stannic disulfide of step S11-S13 preparation through the invention
It is silk ball shape monomer that (scanning electron microscope (SEM) photograph), which shows clearly stannic disulfide, and each silk ball shape monomer includes several petals, adjacent
There is gap between petal.
Next, in step s 2, preparing the bronzing suspension containing stannic disulfide presoma: being prepared by step S1
Silk ball shape stannic disulfide powder about 0.15g is distributed to the 0.02mol/L cobalt cyanic acid potassium solution of about 50ml, and (it can be by about 80mg cobalt cyanogen
It is prepared by sour potassium and about 50ml deionized water) in, magnetic agitation 3h forms stable bronzing suspension, wherein stannic disulfide point
Scattered concentration of polymer solution is about 1.86mg/ml.
In step s3, temperature constant magnetic stirring prepares the compound of stannic disulfide Yu cobalt cyanic acid cobalt: above-mentioned bronzing is hanged
Turbid be added dropwise about 50ml concentration be 0.015mol/L cobalt acetate solution (its can be gone by about 90mg cobalt acetate and about 50ml from
Sub- water preparation) in, constant temperature stirs 4h, forms the compound of stannic disulfide and cobalt cyanic acid cobalt.
In step s 4, the compound of stannic disulfide and cobalt cyanic acid cobalt is washed, be dried in vacuo it is spare after 12h.
In step s 5, high annealing prepares cobaltosic oxide-stannic disulfide nano-complex: by stannic disulfide and cobalt cyanogen
In the compound merging tube type resistance furnace of sour cobalt, the lower annealing of argon gas protection, heating rate is about 8 DEG C/min, after cooling, collects powder
Cobaltosic oxide-stannic disulfide nano-complex is made in end；Wherein, annealing temperature is about 450 DEG C, and anneal about 1.5h, cooled
Journey needs argon gas to protect simultaneously, and sample is collected after 5h.
Referring to figure 5. and Fig. 6, cobaltosic oxide-stannic disulfide of step S1-S5 preparation through the invention are nano combined
The SEM image (scanning electron microscope (SEM) photograph) of object shows clearly the petal that the dispersion of cobaltosic oxide particle is incorporated into silk ball shape stannic disulfide
Stress is applied with the petal to silk ball shape stannic disulfide in gap on surface and between adjacent petal, so that silk ball shape two
The petal pattern of artificial gold changes that the hole of silk ball shape stannic disulfide is made to become smaller.
Comparative example 1
Other than acetic acid cobalt concentration is 0.0075mol/L in step S3, other conditions are the same as embodiment 1.
Comparative example 2
Other than saving step S2-S5, other conditions are the same as embodiment 1, that is, are only prepared for silk ball shape stannic disulfide.
Table 1 and Fig. 7-8 are please referred to, the test of lithium ion battery charge-discharge performance is carried out to embodiment 1 and comparative example 1-2, it will
Material, acetylene black, bonding agent made from embodiment 1 and comparative example 1-2 are that 7:2:1 sizes mixing film in mass ratio, and circular electric is made
Pole piece is dried in vacuo under the conditions of 60 DEG C.
Battery is assemblied in the super purification glove box (Mikrouna, Sukei1220/750) full of argon gas and carries out, with gold
It is diaphragm that belong to lithium piece, which be negative pole, microporous polypropylene membrane Celgard2400 of anode, circular electric pole piece, assembles CR2016 type button
Battery.
Electrolyte uses the mixed solution of the lithium hexafluoro phosphate containing 1mol/L, and the mixed solution is 1:1:1's by volume ratio
Ethylene carbonate, diethyl carbonate and methyl ethyl carbonate are obtained by mixing.
The results are shown in Table 1 for its experiment:
1 charge-discharge performance test result contrast table of table
From table 1 it follows that embodiment 1 and comparative example 1 compare, cobalt source concentration is 0.015mol/L in embodiment 1, is surveyed
The data of the chemical property obtained are more preferable, and discharge capacity is 1343.1mAh/g for the first time, and capacity is maintained at after 50 weeks circulations
Thus 778mAh/g or more illustrates that during compound cobaltosic oxide, cobalt source concentration is more excellent in 0.015mol/L.By implementing
Example 1 and comparative example 2 compare, and cobaltosic oxide-stannic disulfide nano-complex has higher capacity and more compared with stannic disulfide monomer
Good cyclical stability, illustrates that compound cobaltosic oxide plays good modified effect to stannic disulfide.
Fig. 7 is charge/discharge capacity-cycle-index curve of modified vulcanization tin composite material prepared by the embodiment of the present invention 1
Figure.The longitudinal axis is charge/discharge capacity, and horizontal axis is cycle-index, and square line represents charging in figure, and circular lines represent electric discharge, can from figure
To find out, the discharge capacity for the first time of composite material is high, and cycle performance is superior.
Fig. 8 is the specific discharge capacity curve graph that the embodiment of the present invention 1 and comparative example 2 recycle 50 times.The longitudinal axis is discharge capacity,
Horizontal axis is cycle-index, square line (SnS in figure2@Co3O4) represent cobaltosic oxide-stannic disulfide nanometer prepared by embodiment 1
Compound, circular lines (SnS2) stannic disulfide prepared by comparative example 2 is represented, it can be seen from the figure that the addition of cobaltosic oxide
Have a significant impact to the raising of stannic disulfide performance.Discharge capacity is 1249.3mAh/g to pure stannic disulfide for the first time, however capacity attenuation
More obvious, capacity is only 344.4mAh/g after 50 circulations.After compound cobaltosic oxide, discharge capacity is for the first time
1343.1mAh/g, capacity remains within 778.0mAh/g or more after 50 circulations.So the addition of cobaltosic oxide
Compound capacity is not only increased, also has castering action to its cyclical stability.
Although detailed description of the present invention preferred embodiment herein, it is to be understood that the invention is not limited to this
In the specific structure being described in detail and show and step, without departing from the spirit and scope of the present invention can be by this field
Technical staff realize other modifications and variant.In addition, the parameters such as temperature, concentration or time in the present invention can be according to tool
Body use condition is suitably chosen within the scope of the present disclosure.
Claims (9)
1. a kind of cobaltosic oxide-stannic disulfide nano-complex, comprising: molar ratio is the cobaltosic oxide and two of 1:2~1:5
Artificial gold, wherein stannic disulfide is silk ball shape stannic disulfide, and the dispersion of cobaltosic oxide particle is incorporated into silk ball shape stannic disulfide
Stress is applied with the petal to silk ball shape stannic disulfide in gap in petal surface and between adjacent petal, so that silk ball
The petal pattern of shape stannic disulfide changes that the hole of silk ball shape stannic disulfide is made to become smaller, wherein cobaltosic oxide
20%~40% dispersion in grain is incorporated into the petal surface of silk ball shape stannic disulfide, and 60% in cobaltosic oxide particle~
80% dispersion is incorporated into the gap between the adjacent petal of silk ball shape stannic disulfide, so that silk ball shape stannic disulfide is petal
Looks occur to fold and/or crimp.
2. cobaltosic oxide as described in claim 1-stannic disulfide nano-complex, which is characterized in that be including molar ratio
The cobaltosic oxide and stannic disulfide of 1:3~1:4.
3. cobaltosic oxide as claimed in claim 1 or 2-stannic disulfide nano-complex preparation method, which is characterized in that
Include:
(1), prepare silk ball shape stannic disulfide；
(2), ready silk ball shape stannic disulfide 1:100~1:500 in mass ratio is distributed to 0.01~0.03 mol/L
It in cobalt cyanic acid potassium solution, stirs 2~4 hours, forms the suspension containing stannic disulfide presoma；
(3), the suspension containing stannic disulfide presoma prepared 2:1~1:2 addition by volume 0.01~0.03 is rubbed
You/liter cobalt acetate solution in, stir 2~5 hours, formed stannic disulfide and cobalt cyanic acid cobalt compound；
(4), the compound of the stannic disulfide and cobalt cyanic acid cobalt that prepare after washing, is dried in vacuo 8~16 hours；And
(5), the compound of stannic disulfide and cobalt cyanic acid cobalt after drying is annealed under inert gas protection, annealing temperature is
It 350~550 degrees Celsius, anneals 1~3 hour, cobaltosic oxide-stannic disulfide nano-complex is made.
4. cobaltosic oxide as claimed in claim 3-stannic disulfide nano-complex preparation method, which is characterized in that
Preparing silk ball shape stannic disulfide in step (1) includes:
(1.1), 1:1:90~110 are hydrated artificial golds for five in mass ratio and thioacetamide is added to 99% volume ethanol solution
In, 2~4 hours acquisition clear solutions of magnetic agitation；
(1.2), the clear solution obtained carries out vacuum hydro-thermal reaction, and hydrothermal temperature is 160~180 degrees Celsius, when reaction
Between be 12~14 hours, natural cooling after reaction；And
(1.3), it is 5~7 that hydro-thermal reaction product, which is successively cleaned with 99% volume ethanol solution and deionized water to pH value, very
Dry 6~18 hours acquisition silk ball shape stannic disulfides of sky.
5. cobaltosic oxide as claimed in claim 3-stannic disulfide nano-complex preparation method, which is characterized in that
Magnetic agitation is used in step (2), the mass concentration of the suspension containing stannic disulfide presoma of acquisition is 1~2 milligram/milli
It rises.
6. cobaltosic oxide as claimed in claim 3-stannic disulfide nano-complex preparation method, which is characterized in that
Temperature constant magnetic stirring is used in step (3), temperature is set as 25~30 degrees Celsius, and will be outstanding containing stannic disulfide presoma
Turbid is added in cobalt acetate solution by several times.
7. cobaltosic oxide as claimed in claim 3-stannic disulfide nano-complex preparation method, which is characterized in that
In step (4), the stannic disulfide and cobalt cyanic acid cobalt that are successively prepared using 99% volume ethanol solution and deionized water washing
Compound, and vacuum drying temperature is set as 50~60 degrees Celsius.
8. cobaltosic oxide as claimed in claim 3-stannic disulfide nano-complex preparation method, which is characterized in that
Step (5) further comprise annealing after under inert gas protection natural cooling the step of, cooling time be 3~7 hours.
9. cobaltosic oxide as claimed in claim 8-stannic disulfide nano-complex preparation method, which is characterized in that institute
Stating inert gas is argon gas or xenon, and annealing carries out in tube type resistance furnace, and the heating rate in annealing process is set as 5~10
Degrees celsius/minute.
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| CN101950804A (en) * | 2010-07-14 | 2011-01-19 | 北京理工大学 | Method for preparing spherical SnS2 anode material of lithium ion battery |
| CN102437325A (en) * | 2011-12-12 | 2012-05-02 | 中国科学技术大学 | Preparation method of cobaltosic oxide nano cage and cobaltosic oxide nano cage prepared by adopting same |
| CN103991899A (en) * | 2014-06-17 | 2014-08-20 | 合肥工业大学 | Preparation method of porous flowerlike stannic oxide micro-nano structure |
| CN104201232A (en) * | 2014-08-28 | 2014-12-10 | 南京大学 | Tin sulfide nano paper self-assembly microsphere production method and optical detector of microsphere film |
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| CN101950804A (en) * | 2010-07-14 | 2011-01-19 | 北京理工大学 | Method for preparing spherical SnS2 anode material of lithium ion battery |
| CN102437325A (en) * | 2011-12-12 | 2012-05-02 | 中国科学技术大学 | Preparation method of cobaltosic oxide nano cage and cobaltosic oxide nano cage prepared by adopting same |
| CN103991899A (en) * | 2014-06-17 | 2014-08-20 | 合肥工业大学 | Preparation method of porous flowerlike stannic oxide micro-nano structure |
| CN104201232A (en) * | 2014-08-28 | 2014-12-10 | 南京大学 | Tin sulfide nano paper self-assembly microsphere production method and optical detector of microsphere film |
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