CN102146564A - Method for preparing titanium dioxide array film on flexible metallic matrix and application of method in lithium ion battery - Google Patents
Method for preparing titanium dioxide array film on flexible metallic matrix and application of method in lithium ion battery Download PDFInfo
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- CN102146564A CN102146564A CN201110056071XA CN201110056071A CN102146564A CN 102146564 A CN102146564 A CN 102146564A CN 201110056071X A CN201110056071X A CN 201110056071XA CN 201110056071 A CN201110056071 A CN 201110056071A CN 102146564 A CN102146564 A CN 102146564A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing a titanium dioxide array film on a flexible metallic matrix and application of the method in a lithium ion battery. The method comprises the following steps of: soaking the matrix into sulfuric acid cleaning solution to perform ultrasonic cleaning, then soaking the matrix into acetone to perform ultrasonic cleaning, and finally flushing the matrix by using deionized water; adding titanium salt-containing solution and urea into saturated sodium chloride solution to prepare reaction solution, and putting the reaction solution into a stainless steel autoclave with a Teflon lining; soaking the cleaned matrix into the reaction solution, and performing reaction for 2 to 5 hours at the temperature of between 150 and 180 DEG C; sequentially flushing the film obtained after reaction together with the matrix by using sulfuric acid cleaning solution, deionized water and anhydrous ethanol; and performing vacuum drying for 10 to 15 hours at the temperature of between 60 and 100 DEG C to prepare an electrode material. The titanium dioxide nano-rod array film is prepared on the copper/titanium matrix by one-step molding according to the method to form an electrode used for the lithium ion battery; the method is simple, feasible and low in cost; and the film has regular size arrangement, ideal crystallization and large specific surface area, and shows good multiplying power performance on lithium ion intercalation and deintercalation.
Description
Technical field
The present invention relates to a kind of method for preparing titanium dioxide array film, more particularly say, be meant a kind of method that on metallic matrix (copper or titanium metal), prepares titanium dioxide array film, and the application of electrode on lithium ion battery of adopting the inventive method preparation.
Background technology
One of key factor of its overall performance of restriction is a negative material in the lithium ion battery material.The negative material that present commercial lithium ion battery adopted nearly all is carbon/graphite material, and the electropotential of carbon and metallic lithium current potential are very approaching, and when battery overcharge, metallic lithium may be separated out formation dendrite in carbon electrodes, causes safety issue.Simultaneously, Li+ is embedding repeatedly and is deviating from the process, and the carbon material structure can be damaged, thereby causes the decay of capacity.Therefore, searching can embed lithium under than the positive slightly current potential of carbon negative pole current potential, and new negative material cheap and easy to get, safe and reliable and height ratio capacity is a problem highly significant.There are not the problems referred to above in titanium dioxide as lithium ion battery negative material, and advantage such as structural changes is very little in charge and discharge process, degree of polarization is low, thereby has good cycle performance, reversibility and safety performance.Titanium dioxide (TiO
2) be that a kind of easy preparation, cheap, chemistry and thermal characteristics are stable, free of contamination material, obtained at aspects such as solar cell and electrooptical devices using widely.
At present, no matter be rutile mutually or the anatase phase titanium dioxide array, mostly by following different methods preparation: sol-gel is filled the anodic oxidation aluminium formwork method; The chemical meteorology deposition method; Radio frequency sputtering method etc.Can also utilize the direct oxidation metallic titanium matrix to prepare the nano titania array structure, as, hot alkaline solution is directly handled titanium foil and is generated the sodium titanate nano wire, is transformed into titanium dioxide nano thread through ion-exchange and high-temperature heat treatment then; Electrochemical anodic oxidation metal titanium etc.Yet, the prepared array of aforesaid method makes the film crystallization through the high-temperature heat treatment more than 400 ℃ usually, be strong acid or strong basicity at reaction environment perhaps, a lot of metallic matrixes are had very strong corrodibility, this makes choosing of film substrate be subjected to very big restriction.
Summary of the invention
Because TiO in the present liquid phase environment
2Array preparation need be in strong acid or strong alkali environment, and therefore product needed is difficult to prepare TiO through pyroprocessing on metallic matrix
2Array has limited the application of this material on lithium ion battery.One of purpose of the present invention is to propose a kind of method for preparing titanium dioxide array film on metallic matrix, and this method reaction conditions gentleness is simple and easy to do; The present invention goes up the TiO of preparation at Copper Foil or titanium foil (can be used as affluxion body in lithium ion batteries)
2Array film can not need to add any conductive agent and binding agent directly as lithium ion battery negative, avoided the impurity that exists between common powder body material and collector interface, and loose contact influences the problem of charge-conduction.
A kind of method that on the matrix of flexible metal, prepares titanium dioxide array film of the present invention, it has the following step:
Step 1: clean the flexible metal matrix
The flexible metal matrix is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind ultrasonic cleaning 3～10min, immerse acetone (C again
3H
6O) behind ultrasonic cleaning 8～20min, take out in, the impurity with deionized water rinsing removal matrix surface obtains clean matrix;
Described flexible metal matrix is Copper Foil, titanium foil and copper, titanium, titanium alloy or stainless steel sheet material;
Step 2: make first mixed solution
The solubility titanium salt is dissolved in formation first mixed solution in saturated sodium-chloride (NaCl) solution;
Consumption: the volumetric molar concentration of titanium salt is 0.05～0.3M in first mixed solution;
The solubility titanium salt is titanous chloride (TiCl
3), titanium tetrachloride (TiCl
4), titanyl sulfate (TiOSO
4) or titanium sulfate (Ti (SO
4)
2);
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 5-15g/L in second mixed solution;
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of being with the Teflon liner, and clean matrix oblique cutting is immersed in second mixed solution, the sealing back makes preform electrode in reaction under 150～180 ℃ after 2～5 hours;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 10～30min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 3～5 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3～5 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, 60～100 ℃ of temperature dry 10～15 hours, promptly obtain having the electrode of titanium dioxide array rete.
The present invention prepares the titanium dioxide array film method on the matrix of flexible metal advantage is:
1. preparation condition gentleness of the present invention, the reaction times is short, and method is simple, has avoided the corrosion of reaction environment to metallic matrix as much as possible.
2. the prepared TiO of the present invention
2Nanometer stick array is a rutile structure the most stable on the thermodynamics, and size is even, and crystalline orientation unanimity, all nanometer rod are all along the direction growth with higher li ionic diffusion coefficient.
3. the present invention is at metallic matrix (Copper Foil or titanium foil) one step growth lithium ion battery negative material TiO2 array, through cutting, can be directly used in the electrode of lithium ion battery, do not need to add any conductive agent or binding agent, avoided the destruction of impurity introducing, simplified the preparation process of li-ion electrode simultaneously battery performance.
4. the prepared lithium ion battery electrode material of the present invention has still kept stable charge-discharge performance under than high magnification (about 2C), circulates after 100 times, and capacity is almost undamped.
Description of drawings
Fig. 1 is that the scanning electron microscope diagram sheet takes place in the field of the lithium ion battery negative material of embodiment 1 preparation.
Fig. 2 is the x-ray diffraction pattern of the titanium dioxide array film of embodiment 1 preparation, and among the figure, copper refers to the diffraction peak of copper, and all the other are the red schorl phase titanium dioxide diffraction peak;
Fig. 3 is the cycle performance curve of the titanium dioxide array film of embodiment 1 preparation as lithium ion cell electrode.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
A kind of method that on the matrix of flexible metal, prepares titanium dioxide array film of the present invention, this method may further comprise the steps:
Step 1: clean the flexible metal matrix
The flexible metal matrix is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind ultrasonic cleaning 3～10min, immerse acetone (C again
3H
6O) behind ultrasonic cleaning 8～20min, take out in, the impurity with deionized water rinsing removal matrix surface obtains clean matrix;
Described flexible metal matrix is Copper Foil, titanium foil and copper, titanium, titanium alloy or stainless steel sheet material;
Step 2: make first mixed solution
The solubility titanium salt is dissolved in formation first mixed solution in saturated sodium-chloride (NaCl) solution;
Consumption: the volumetric molar concentration of titanium salt is 0.05～0.3M in first mixed solution;
The solubility titanium salt is titanous chloride (TiCl
3), titanium tetrachloride (TiCl
4), titanyl sulfate (TiOSO
4) or titanium sulfate (Ti (SO
4)
2);
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 5-15g/L in second mixed solution;
In the present invention, adopt urea ((NH
2)
2CO), help the growth of crystal forming core, and prevent the metallic matrix corrosion as forming core promotor and metal inhibitor.
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of band Teflon liner, and clean matrix oblique cutting immersed in second mixed solution, the sealing back makes titanium dioxide array rete (being also referred to as preform electrode) in reaction under 150～180 ℃ after 2～5 hours on metallic matrix;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 10～30min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 3～5 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3～5 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, 60～100 ℃ of temperature dry 10～15 hours, promptly obtain having the electrode of titanium dioxide array rete;
Step 6: as counter electrode, the electrode assembling that makes with step 5 becomes battery with the lithium sheet, and electrolytic solution is LiPF
6/ EC+DEC (volume ratio 1: 1).
Embodiment 1 prepares titanium dioxide array film on Copper Foil
Step 1: clean Copper Foil
Copper Foil is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind the ultrasonic cleaning 5min, immerse acetone (C again
3H
6O) behind the ultrasonic cleaning 10min, take out in, the impurity with deionized water rinsing removal matrix surface obtains clean matrix;
Step 2: make first mixed solution
With titanous chloride (perhaps titanium tetrachloride (TiCl
4)) be dissolved in saturated sodium-chloride (NaCl) solution and form first mixed solution;
Consumption: the volumetric molar concentration of titanium salt is 0.1M in first mixed solution;
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 12g/L in second mixed solution;
In the present invention, adopt urea ((NH
2)
2CO), help the growth of crystal forming core, and prevent the metallic matrix corrosion as forming core promotor and metal inhibitor.
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of band Teflon liner, and clean matrix oblique cutting immersed in second mixed solution, the sealing back makes titanium dioxide array rete (being also referred to as preform electrode) in reaction under 150 ℃ after 3 hours on metallic matrix;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 10min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 3 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, the 80 ℃ of temperature dry 15 hours, promptly obtain having the electrode of titanium dioxide array rete;
Step 6: as counter electrode, the electrode assembling that makes with step 5 becomes battery with the lithium sheet, and electrolytic solution is LiPF
6/ EC+DEC (volume ratio 1: 1).The electrode with titanium dioxide array rete that embodiment 1 is obtained adopts field emission scanning electron microscope to carry out macro morphology observation, SEM photo such as Fig. 1.Film is the monodimension nano stick array structure among the figure, and its mean diameter is about 100nm, and length is about 1 μ m.From visual inspection, the copper foil surface of light has covered the film of one deck white, and this film combines with Copper Foil well, can be with the Copper Foil bending, and structure can not destroyed.
The electrode with titanium dioxide array rete that embodiment 1 is obtained adopts the X-ray diffraction analysis instrument to carry out structural analysis, as shown in Figure 2, experimental result shows that membrane structure is titanium dioxide structure a---rutile titanium dioxide the most stable on the thermodynamics, the array well-crystallized.
In order to check titanium dioxide array film that embodiment 1 makes advantage as lithium ion cell electrode, with metallic lithium as negative pole, titanium dioxide array film is as positive pole, the cycle performance of the titanium dioxide array film that celguard 2300 obtains as barrier film assembling simulated battery test implementation example 1.As Fig. 3, battery is (100 μ Ahcm under higher current density
-2, ≈ 2C), showed excellent cycle performance, the reversible specific capacity of battery is 45 μ Ahcm
-2, the enclosed pasture efficient of battery is higher than 95%, and it is almost undamped after 100 times to circulate, and has embodied satisfactory stability, illustrates that the titanium dioxide array film material has an application potential on power lithium-ion battery.
Embodiment 2 prepares titanium dioxide array film on titanium foil
Step 1: clean titanium foil
Titanium foil is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind the ultrasonic cleaning 10min, immerse acetone (C again
3H
6O) behind the ultrasonic cleaning 8min, take out in, remove the impurity on titanium foil surface, obtain clean titanium foil with deionized water rinsing;
Step 2: make first mixed solution
With titanyl sulfate (TiOSO
4) be dissolved in saturated sodium-chloride (NaCl) solution and form first mixed solution;
Consumption: the volumetric molar concentration of titanium salt is 0.2M in first mixed solution;
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 8g/L in second mixed solution;
In the present invention, adopt urea ((NH
2)
2CO), help the growth of crystal forming core, and prevent the metallic matrix corrosion as forming core promotor and metal inhibitor.
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of band Teflon liner, and clean matrix oblique cutting immersed in second mixed solution, the sealing back makes titanium dioxide array rete (being also referred to as preform electrode) in reaction under 170 ℃ after 5 hours on metallic matrix;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 15min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 3 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, the 60 ℃ of temperature dry 15 hours, promptly obtain having the electrode of titanium dioxide array rete;
Step 6: as counter electrode, the electrode assembling that makes with step 5 becomes battery with the lithium sheet, and electrolytic solution is LiPF
6/ EC+DEC (volume ratio 1: 1).
Adopt the mode identical with embodiment 1 to carry out the charge-discharge test of battery: battery is (100 μ Ahcm under higher current density
-2), having showed excellent cycle performance, the reversible specific capacity of battery is 40 μ Ahcm
-2, the enclosed pasture efficient of battery is higher than 95%, and it is almost undamped after 100 times to circulate, and has embodied satisfactory stability.Compare with embodiment 1, the consumption that embodiment 2 reduces urea still can access well-grown nano titania array film to 8g/L.
Embodiment 3 prepares titanium dioxide array film on stainless steel substrates
Step 1: clean stainless steel substrates
Stainless steel substrates is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind the ultrasonic cleaning 6min, immerse acetone (C again
3H
6O) behind the ultrasonic cleaning 15min, take out in, remove the impurity on stainless steel substrates surface, obtain clean stainless steel substrates with deionized water rinsing;
Stainless steel substrates size (length and width are thick): 10cm * 3cm * 0.2cm
Step 2: make first mixed solution
With titanium sulfate (Ti (SO
4)
2) be dissolved in saturated sodium-chloride (NaCl) solution and form first mixed solution;
Consumption: the volumetric molar concentration of titanium salt is 0.15M in first mixed solution;
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 15g/L in second mixed solution;
In the present invention, adopt urea ((NH
2)
2CO), help the growth of crystal forming core, and prevent the metallic matrix corrosion as forming core promotor and metal inhibitor.
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of band Teflon liner, and clean matrix oblique cutting immersed in second mixed solution, the sealing back makes titanium dioxide array rete (being also referred to as preform electrode) in reaction under 180 ℃ after 5 hours on metallic matrix;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 30min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 4 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, the 80 ℃ of temperature dry 12 hours, promptly obtain having the electrode of titanium dioxide array rete;
Step 6: as counter electrode, the electrode assembling that makes with step 5 becomes battery with the lithium sheet, and electrolytic solution is LiPF
6/ EC+DEC (volume ratio 1: 1).
Adopt the mode identical with embodiment 1 to carry out the charge-discharge test of battery: battery is (100 μ Ahcm under higher current density
-2), having showed excellent cycle performance, the reversible specific capacity of battery is 35 μ Ahcm
-2, the enclosed pasture efficient of battery is higher than 90%, and it is almost undamped after 100 times to circulate, and has embodied satisfactory stability.
Claims (4)
1. method for preparing titanium dioxide array film on the matrix of flexible metal is characterized in that the following step is arranged:
Step 1: clean the flexible metal matrix
The flexible metal matrix is immersed 0.5M sulfuric acid (H
2SO
4) in the washing lotion behind ultrasonic cleaning 3～10min, immerse acetone (C again
3H
6O) behind ultrasonic cleaning 8～20min, take out in, the impurity with deionized water rinsing removal matrix surface obtains clean matrix;
Step 2: make first mixed solution
The solubility titanium salt is dissolved in formation first mixed solution in saturated sodium-chloride (NaCl) solution;
Consumption: the volumetric molar concentration of titanium salt is 0.05～0.3M in first mixed solution;
The solubility titanium salt is titanous chloride (TiCl
3), titanium tetrachloride (TiCl
4), titanyl sulfate (TiOSO
4) or titanium sulfate (Ti (SO
4)
2);
Step 3: make second mixed solution
In first mixed solution, add urea ((NH
2)
2CO) form second mixed solution;
Consumption: the mass concentration of urea is 5～15g/L in second mixed solution;
Step 4: system preform electrode
Second mixed solution is put into the stainless steel cauldron of being with the Teflon liner, and clean matrix oblique cutting is immersed in second mixed solution, the sealing back makes preform electrode in reaction under 150～180 ℃ after 2～5 hours;
Step 5: fixture has the electrode of titanium dioxide array rete
Preform electrode soaked 10～30min in the 0.5M sulfuric acid lotion after, behind deionized water rinsing 3～5 times, use dehydrated alcohol (C again
2H
6O) after the flushing 3～5 times, take out, place vacuum drying oven, and be 1.33 * 10 in vacuum tightness
-4Under MPa, 60～100 ℃ of temperature dry 10～15 hours, promptly obtain having the electrode of titanium dioxide array rete.
2. the application of the electrode with titanium dioxide array rete on lithium ion battery that claim 1 is made is characterized in that: as counter electrode, the electrode assembling that step 5 makes becomes battery with the lithium sheet, and electrolytic solution is LiPF
6/ EC+DEC (volume ratio 1: 1).
3. the application of the electrode with titanium dioxide array rete on lithium ion battery that makes according to claim 2 is characterized in that: the reversible specific capacity of battery is 30～50 μ Ahcm
-2, the enclosed pasture efficient of battery is higher than 90%～95%, and it is almost undamped after 100 times to circulate, and has embodied satisfactory stability.
4. the method for preparing titanium dioxide array film on the matrix of flexible metal according to claim 1 is characterized in that: the flexible metal matrix is Copper Foil, titanium foil and copper, titanium, titanium alloy or stainless steel sheet material.
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| CN103103596A (en) * | 2013-01-14 | 2013-05-15 | 北京工业大学 | Preparation method of coaxial titanium dioxide nanotube and nanorod composite array |
| CN103107307A (en) * | 2013-01-31 | 2013-05-15 | 苏州大学 | Water-solution lithium ion battery negative pole material and preparation method thereof |
| CN103178243A (en) * | 2013-03-27 | 2013-06-26 | 北京大学 | Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material |
| CN106099094A (en) * | 2016-06-17 | 2016-11-09 | 武汉科技大学 | A kind of self-supporting fexible film of beading lithium titanate nano-particle composition and preparation method thereof |
| CN107596735A (en) * | 2017-11-06 | 2018-01-19 | 吉林大学 | A kind of preparation facilities and method of super-amphiphobic automatically cleaning water-oil separating material |
| CN111554913A (en) * | 2020-05-20 | 2020-08-18 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN112675859A (en) * | 2021-01-28 | 2021-04-20 | 华南农业大学 | Foam nickel-based titanium dioxide nano composite material and preparation method and application thereof |
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| CN103103596A (en) * | 2013-01-14 | 2013-05-15 | 北京工业大学 | Preparation method of coaxial titanium dioxide nanotube and nanorod composite array |
| CN103103596B (en) * | 2013-01-14 | 2015-07-01 | 北京工业大学 | Preparation method of coaxial titanium dioxide nanotube and nanorod composite array |
| CN103107307A (en) * | 2013-01-31 | 2013-05-15 | 苏州大学 | Water-solution lithium ion battery negative pole material and preparation method thereof |
| CN103178243A (en) * | 2013-03-27 | 2013-06-26 | 北京大学 | Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material |
| CN106099094A (en) * | 2016-06-17 | 2016-11-09 | 武汉科技大学 | A kind of self-supporting fexible film of beading lithium titanate nano-particle composition and preparation method thereof |
| CN106099094B (en) * | 2016-06-17 | 2019-02-05 | 武汉科技大学 | A kind of self-supporting fexible film and preparation method thereof of beading lithium titanate nano particle composition |
| CN107596735A (en) * | 2017-11-06 | 2018-01-19 | 吉林大学 | A kind of preparation facilities and method of super-amphiphobic automatically cleaning water-oil separating material |
| CN111554913A (en) * | 2020-05-20 | 2020-08-18 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN111554913B (en) * | 2020-05-20 | 2021-06-15 | 佛山科学技术学院 | Multilayer titanium dioxide mesoporous film electrode material and preparation method and application thereof |
| CN112675859A (en) * | 2021-01-28 | 2021-04-20 | 华南农业大学 | Foam nickel-based titanium dioxide nano composite material and preparation method and application thereof |
| CN114361387A (en) * | 2022-01-12 | 2022-04-15 | 四川大学 | Self-supporting B-type titanium dioxide nano long strip network electrode and preparation method thereof |
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Application publication date: 20110810 |