CN101764213B - Method for preparing stannic oxide battery anode material on carbon nano tube by using electro-deposition process - Google Patents

Method for preparing stannic oxide battery anode material on carbon nano tube by using electro-deposition process Download PDF

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CN101764213B
CN101764213B CN201010033606A CN201010033606A CN101764213B CN 101764213 B CN101764213 B CN 101764213B CN 201010033606 A CN201010033606 A CN 201010033606A CN 201010033606 A CN201010033606 A CN 201010033606A CN 101764213 B CN101764213 B CN 101764213B
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minutes
electro
deposition
pole piece
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CN201010033606A
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CN101764213A (en
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张世超
冯涛
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北京航空航天大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a method for preparing a stannic oxide battery anode material on a carbon nano tube by using an electro-deposition process. The method comprises the steps of: making electro-deposition solution, treating the solution with water bath, preparing the carbon nano tube pole piece, pressing on a foam nickel base, putting the base carrying the carbon nano tube pole piece into the electro-deposition solution so as to perform vacuum treatment, and then perform the electro-deposition treatment under a constant current on the vacuumized pole piece so as to acquire the battery anode material on the carbon nano tube carrying the stannic oxide. The battery anode material prepared by using the method has higher power property and has a quality specific capacity kept between 350 and 450 F/g under a high scanning speed of 200 mV/s. The material applied in a super capacitor has higher volumetric properties, excellent cycling stability and long cycling life, first discharging specific capacity ranged between 410 and 588 F/g under a constant current density of 15 A/g, cycling times more than 5000 times and specific capacity retention rate ranged between 90 to 95 percent.

Description

A kind of method that adopts electrodeposition process on CNT, to prepare stannic oxide battery anode material
Technical field
The present invention relates to a kind of electrode battery preparation methods, more particularly say, be meant a kind of method that adopts electrodeposition process on CNT, to prepare tin dioxide material.
Background technology
CNT is the nanoscale tubular material that is curled and formed by single or multiple lift graphite face; Since its unique hollow structure, good electrical conductivity, big specific area and the nanoscale network configuration that is entwined alternately; When using as electrode material for super capacitor; Can pass through the electric double layer capacitance energy storage, have than high-specific-power and excellent cycle performance, but specific capacity be lower.Tin ash is the n type semiconductor oxide with wide energy gap, and is cheap, has good environment friendly; During as electrode material for super capacitor, can react energy storage through the quick faraday in surface, specific capacity is higher; But the invertibity of electrode reaction is relatively poor, and power-performance is relatively poor.
In order better to bring into play the advantage of CNT; Power-performance and the cycle performance of while in order to improve stannic oxide electrode; The load stannic oxide particle constitutes combination electrode material on CNT; Not only can give full play to the advantage of electric double layer capacitance and pseudo capacitance energy storage, can obtain high-specific-power and high-energy-density simultaneously, therefore be considered to the desirable electrode material of high-power super capacitor.
With the composite material of tin ash and the CNT electrode material as lithium ion battery and ultracapacitor, its preparation method mainly is sol-gal process, hydro thermal method, homogeneous precipitation method etc.These preparation method's flow processs are loaded down with trivial details and adhesion tin ash and CNT is little, are prone to take place the phenomenon of particle agglomeration when using as electrode material.
Summary of the invention
In order to overcome above-mentioned preparation method's defective; The present invention proposes a kind of method that adopts electrodeposition process on CNT, to prepare stannic oxide battery anode material; This method is through loading current in plating bath; Charged particle in the plating bath is moved on the CNT matrix by influence, and generation redox reaction and deposition are separated out near matrix surface, thereby on the CNT matrix, prepare stannic oxide particle.The stannic oxide battery anode material of preparing is to adopt the electrodeposition process one-step shaping directly to be deposited on tin ash on the CNT.
Employing electrodeposition process of the present invention prepares the method for tin dioxide material on CNT, comprise the steps:
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 50 ℃~90 ℃ water bath heat preservations under the condition after 30 minutes~120 minutes, for use;
Add the stannous chloride of 0.15g~2.5g, the nitric acid of 0.68ml~6.8ml and the sodium nitrate of 2g~10g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 1g~3g and the PTFE of 0.05g~0.15g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 60 ℃~150 ℃ following dried after 10 minutes~50 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 30 ℃~80 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 10 minutes~60 minutes, obtain first intermediate;
This step suction is 0.1MPa~0.3MPa;
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtains second intermediate after 5 minutes~45 minutes under 0.1mA~2mA condition;
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 1~3 hour, take out, and to put into temperature be 30 ℃~80 ℃ down after dry 8 hours~12 hours, obtain the cell positive material that load on the CNT has tin ash.
The present invention adopts electrodeposition process on CNT, to prepare the advantage of stannic oxide battery anode material method:
1. adopt electrodeposition process on CNT, to prepare tin dioxide material.
2. electro-deposition method technology is easy, and is with low cost.
3. the prepared tin dioxide material crystallization of electro-deposition method is careful, and particle size and macro morphology are controlled.
4. load has the cell positive material of tin ash on the prepared CNT of electro-deposition method, is used for ultracapacitor and has high volumetric properties, and specific discharge capacity is the highest can to reach 588F/g.
5. load has the cell positive material of tin ash on the prepared CNT of electro-deposition method, is used for ultracapacitor and has good power-performance, and at high sweep speed 200mV/s, specific discharge capacity still keeps 450F/g.
6. load has the cell positive material of tin ash on the prepared CNT of electro-deposition method; Be used for ultracapacitor and have good cyclical stability and long cycle life; Under constant current density 15A/g; Cycle-index can reach more than 5000 times, and the specific capacity conservation rate is 90~95%.
Description of drawings
Fig. 1 is the voltage of electro-deposition among the embodiment 1 and the graph of a relation of sedimentation time.
Fig. 2 adopts load on the CNT that embodiment 1 method makes that the surface topography map (SEM) of the cell positive material of tin ash is arranged.
Fig. 3 adopts load on the CNT that embodiment 1 method makes that the specific capacity curve of cell positive material under different scanning speed of tin ash arranged.
Fig. 4 adopts load on the CNT that embodiment 1 method makes that the specific capacity-cycle-index curve of the cell positive material of tin ash is arranged.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further detailed description below.
A kind of method that adopts electrodeposition process on CNT, to prepare stannic oxide battery anode material of the present invention comprises the steps:
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 50 ℃~90 ℃ water bath heat preservations under the condition after 30 minutes~120 minutes, for use;
Add the stannous chloride of 0.15g~2.5g, the nitric acid of 0.68ml~6.8ml and the sodium nitrate of 2g~10g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 1g~3g and the PTFE of 0.05g~0.15g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 60 ℃~150 ℃ following dried after 10 minutes~50 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 30 ℃~80 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 10 minutes~60 minutes, obtain first intermediate;
This step suction is 0.1MPa~0.3MPa;
In the present invention, the purpose that vacuumizes is in order to let the tin ion in the electric depositing solution infiltrate through in the CNT pole piece of porous, to improve the uniformity of electro-deposition tin ash.
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtains second intermediate after 5 minutes~45 minutes under 0.1mA~2mA condition;
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 1~3 hour, take out, and to put into temperature be 30 ℃~80 ℃ down after dry 8 hours~12 hours, obtain the cell positive material that load on the CNT has tin ash.
In order to test the capacitive property that adopts load on the CNT that the inventive method makes that the cell positive material of tin ash is arranged; Under vacuum state; In the electrolyte (concentration 7mol/L) of ultracapacitor, soaked 10~24 hours; Pack into after the taking-up in the analog capacitor, insert battery test system (adopt Shenzhen new Weir Electronics Co., Ltd. to produce BTS-5V/10mA is arranged) and test.
Embodiment 1
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 85 ℃ of water bath heat preservations under the condition after 60 minutes, for use;
The stannous chloride, the nitric acid of 0.27ml and the sodium nitrate of 4.5g that add 0.38g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 2g and the PTFE of 0.1g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 100 ℃ of following dried after 50 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 60 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 30 minutes, obtain first intermediate;
This step suction is 0.1MPa;
In the present invention, the purpose that vacuumizes is in order to let the tin ion in the electric depositing solution infiltrate through in the CNT pole piece of porous, to improve the uniformity of electro-deposition tin ash.
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtained second intermediate after 30 minutes under the 0.1mA condition;
In electrodeposition process of the present invention, the relation of electrodeposition time and voltage is as shown in Figure 1, and under constant depositing current density, along with the increase of sedimentation time, deposition voltage reaches a stationary value gradually.
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 2 hours, take out, and to put into temperature be 60 ℃ down after dry 12 hours, obtain the cell positive material that load on the CNT has tin ash.
Adopt SEM to have the cell positive material of tin ash to carry out morphology analysis to load on the CNT; As shown in Figure 2, on the surface that is distributed in each root CNT of tin oxide nano particles disperse, make the caliber of CNT slightly increase; But do not block the loose structure that CNT twines formation alternately; Help electrolyte ion and in combination electrode, move, thereby accelerate the speed of electrode reaction, and help to improve the cyclical stability of combination electrode.
In order to test the capacitive property that adopts load on the CNT that the inventive method makes that the cell positive material of tin ash is arranged; Under vacuum state; In the electrolyte (concentration 7mol/L) of ultracapacitor, soaked 12 hours; Pack into after the taking-up in the analog capacitor, insert battery test system (adopt Shenzhen new Weir Electronics Co., Ltd. to produce BTS-5V/10mA is arranged) and test.
As shown in Figure 3; Specific discharge capacity under 10mV/s is 590F/g; Along with the increase of sweep speed, specific discharge capacity presents the trend of reduction, but under the high sweep speed of 200mV/s, still obtains the height ratio capacity of 450F/g; It is thus clear that load has the cell positive material of tin ash to have good power-performance as electrode of super capacitor on CNT, is fit to carry out high current charge-discharge.
As shown in Figure 4; Under constant current density 15A/g; Discharge capacity is 588F/g first; Circulating, specific capacity still remains on 540F/g after 5000 times, and capability retention is more than 92%, visible on CNT load have the cell positive material of tin ash to have high volumetric properties and good cyclical stability as electrode of super capacitor.
Embodiment 2
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 50 ℃ of water bath heat preservations under the condition after 120 minutes, for use;
The stannous chloride, the nitric acid of 6.8ml and the sodium nitrate of 2g that add 2.5g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 3g and the PTFE of 0.15g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 150 ℃ of following dried after 10 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 30 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 60 minutes, obtain first intermediate;
This step suction is 0.1MPa;
In the present invention, the purpose that vacuumizes is in order to let the tin ion in the electric depositing solution infiltrate through on the CNT pole piece of porous, to improve the uniformity of electro-deposition tin ash.
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtained second intermediate after 5 minutes under the 2mA condition;
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 3 hours, take out, and to put into temperature be 30 ℃ down after dry 10 hours, obtain the cell positive material that load on the CNT has tin ash.
In order to test the capacitive property that adopts load on the CNT that the inventive method makes that the cell positive material of tin ash is arranged; Under vacuum state; In the electric depositing solution (concentration 7mol/L) of ultracapacitor, soaked 12 hours; Pack into after the taking-up in the analog capacitor, insert battery test system (adopt Shenzhen new Weir Electronics Co., Ltd. to produce BTS-5V/10mA is arranged) and test.
According to implementing the electrode anode that 2 preparation methods make, the specific discharge capacity under 10mV/s is 420F/g, and along with the increase of sweep speed, specific discharge capacity presents the trend of reduction, but under the high sweep speed of 200mV/s, still obtains the height ratio capacity of 380F/g.Under constant current density 15A/g; Discharge capacity is 438F/g first; Circulating, specific capacity still remains on 394F/g after 5000 times; Capability retention is 90%, it is thus clear that load has the cell positive material of tin ash to have higher power-performance, good volumetric properties and the cycle life of growing as electrode of super capacitor on CNT
Embodiment 3
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 70 ℃ of water bath heat preservations under the condition after 90 minutes, for use;
The stannous chloride, the nitric acid of 0.68ml and the sodium nitrate of 9g that add 0.15g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 1g and the PTFE of 0.05g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 80 ℃ of following dried after 30 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 80 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 15 minutes, obtain first intermediate;
This step suction is 0.3MPa;
In the present invention, the purpose that vacuumizes is in order to let the tin ion in the electric depositing solution infiltrate through on the CNT pole piece of porous, to improve the uniformity of electro-deposition tin ash.
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtained second intermediate after 20 minutes under the 0.5mA condition;
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 1 hour, take out, and to put into temperature be 80 ℃ down after dry 8 hours, obtain the cell positive material that load on the CNT has tin ash.
In order to test the capacitive property that adopts load on the CNT that the inventive method makes that the cell positive material of tin ash is arranged; Under vacuum state; In the electrolyte (concentration 7mol/L) of ultracapacitor, soaked 12 hours; Pack into after the taking-up in the analog capacitor, insert battery test system (adopt Shenzhen new Weir Electronics Co., Ltd. to produce BTS-5V/10mA is arranged) and test.
According to implementing the cell positive material that 3 preparation methods make; Specific discharge capacity under 10mV/s is 410F/g; Along with the increase of sweep speed, specific discharge capacity presents the trend of reduction, but under the high sweep speed of 200mV/s, still obtains the height ratio capacity of 368F/g; Under constant current density 15A/g; Discharge capacity is 426F/g first; Circulating, specific capacity still remains on 400F/g after 5000 times; Capability retention is 94%, and visible tin dioxide/carbon nano tube composite material has higher power-performance, good volumetric properties and the cycle life of growing as electrode of super capacitor.

Claims (1)

1. method that adopts electrodeposition process on CNT, to prepare stannic oxide battery anode material is characterized in that including the following step:
The first step: configuration electric depositing solution:
Electric depositing solution is by stannous chloride SnCl 2, nitric acid HNO 3, sodium nitrate NaNO 3Form with deionized water, then electric depositing solution being placed temperature is 50 ℃~90 ℃ water bath heat preservations under the condition after 30 minutes~120 minutes, for use;
Add the stannous chloride of 0.15g~2.5g, the nitric acid of 0.68ml~6.8ml and the sodium nitrate of 2g~10g in the deionized water of consumption: 100ml;
Second step: preparation CNT pole piece:
Solvent: ethanol
Raw material: CNT;
Binding agent: mass percent concentration is 60% PTFE (polytetrafluoroethylene);
Add the CNT of 1g~3g and the PTFE of 0.05g~0.15g in the ethanol of consumption: 100ml;
With above raw materials mix evenly after, be 60 ℃~150 ℃ following dried after 10 minutes~50 minutes in temperature, take out, obtain having certain flexible dope;
Then, be constantly to roll pressure on the heated at constant temperature plate under 30 ℃~80 ℃ to this dope in temperature, and roll formation CNT pole piece through double-roll rolling mill;
At last, the CNT pole piece is pressed together on the sheet nickel foam, makes the CNT substrate that is used for electro-deposition;
The 3rd step: the electric depositing solution that the first step makes is put in the CNT substrate that second step obtained, vacuumized dipping after 10 minutes~60 minutes, obtain first intermediate;
Suction is 0.1MPa~0.3MPa;
The 4th step: will put into the electric depositing solution that the first step makes through first intermediate that the 3rd step obtained, and loading current density is that electrodeposition process obtains second intermediate after 5 minutes~45 minutes under 0.1mA~2mA condition;
The 5th step: after the 4th second intermediate that obtain of step put into deionized water and soak 1~3 hour, take out, and to put into temperature be 30 ℃~80 ℃ down after dry 8 hours~12 hours, obtain the cell positive material that load on the CNT has tin ash.
CN201010033606A 2010-01-04 2010-01-04 Method for preparing stannic oxide battery anode material on carbon nano tube by using electro-deposition process CN101764213B (en)

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