CN112563468B - Lithium ion battery cathode nanofiber composite material and preparation method and application thereof - Google Patents
Lithium ion battery cathode nanofiber composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof, wherein the method comprises the following steps: using SnO containing 2 Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning 2 a/C @ Ni nanofiber precursor; the SnO 2 SnO is obtained by oxidizing and carbonizing a/C @ Ni nanofiber precursor 2 the/C @ Ni nano-fiber composite material is the lithium ion battery negative electrode nano-fiber composite material. SnO of the present invention 2 the/C @ Ni nanofiber composite material is used as a lithium ion battery cathode material, the conductivity and the structural stability are remarkably improved, and the composite material has good electrochemical stability and rate capability and commercial application value.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof.
Background
Tin dioxide (SnO) 2 ) The lithium ion battery cathode material is considered to be the most promising material to replace the commercial graphite cathode material, becomes one of the materials of the next generation of novel lithium ion battery cathode material, and has the advantages of high theoretical specific capacity, wide environmental storage, environmental friendliness, no pollution, higher safety and the like. However, SnO 2 The inherent electron transport performance of the material is poor, and the material is charged and dischargedSnO is caused by severe volume expansion and contraction 2 The phenomena of pulverization and secondary agglomeration are continuously generated in the charge and discharge processes of the material, so that the electrochemical activity is lost, and the performance is rapidly attenuated.
To solve SnO 2 In view of the above problems of the negative electrode material, many researches and attempts have been made to combine the negative electrode material with a carbon material to prepare a nano structure, a hollow or porous structure, etc., but the current manufacturing method has high preparation cost and is difficult to realize large-scale commercial production; in addition, in the prior art, the problems of poor electrochemical stability and rate capability of the prepared battery cathode material and the like are urgently needed to be further improved.
Disclosure of Invention
Therefore, the invention provides a lithium ion battery cathode nanofiber composite material and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the embodiment of the invention provides a preparation method of a lithium ion battery cathode nanofiber composite material, which comprises the following steps: using SnO containing 2 Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning 2 a/C @ Ni nanofiber precursor;
the SnO is 2 SnO is obtained by oxidizing and carbonizing a/C @ Ni nanofiber precursor 2 the/C @ Ni nanofiber composite material is the lithium ion battery cathode nanofiber composite material.
In one embodiment of the invention, the SnO 2 The preparation method of the/C nanosphere precursor comprises the following steps:
adding potassium stannate into water, stirring and carrying out ultrasonic treatment until the potassium stannate is completely dissolved to obtain a potassium stannate solution, adding glucose, continuously stirring until the potassium stannate is completely dissolved to obtain a first solution, adding the first solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in an explosion-proof oven at 180 ℃, reacting for 4 hours, washing, centrifuging and drying a reaction product to obtain the SnO 2 a/C nanosphere precursor.
Wherein, in the first solution, the mass fraction of the potassium stannate is 1-10%, and the mass ratio of the glucose to the potassium stannate is 0.5-10.
In an embodiment of the present invention, the second solution is prepared by:
adding Polyacrylonitrile (PAN) into N, N-Dimethylformamide (DMF), stirring at 80 deg.C for 30min to dissolve completely, adding the SnO 2 And stirring the/C nanosphere precursor for 30min to obtain the second solution.
In one embodiment of the invention, in the second solution, the mass fraction of polyacrylonitrile is 1% -30%, and the SnO is 2 The mass ratio of the/C nanosphere precursor to the polyacrylonitrile is 0.1-5.
In an embodiment of the present invention, the third solution is prepared by:
adding polyvinylpyrrolidone (PVP) into N, N-Dimethylformamide (DMF), stirring at 60 deg.C for 30min until PVP is completely dissolved, adding nickel acetylacetonate, and stirring for 30min to obtain a third solution;
wherein, in the third solution, the PVP accounts for 10-30% by mass; the mass ratio of the nickel acetylacetonate to the PVP is 0.01-5.
In one embodiment of the present invention, the coaxial electrospinning conditions are:
the inner layer pipeline is filled with the second solution, the outer layer pipeline is filled with the third solution, the voltage is 5-50kV, and the receiving speed of the roller is 0-100r min -1 Push-injection pushing speed of 0.1-10mL h -1 The distance between the electrospinning needle head and the receiver is 5-30cm, and the electrospinning time is 1-100 h.
In one embodiment of the present invention, the oxidation treatment process is:
the SnO is 2 The precursor of the/C @ Ni nano-fiber is put in the air at the temperature of 1-10 ℃ for min -1 The temperature rising speed is gradually increased to 150-300 ℃, and the temperature is kept for 0.5-3 h.
In one embodiment of the present invention, the carbonization process is:
oxidizing the treated SnO 2 Putting the/C @ Ni nanofiber precursor in an inert gas atmosphere at the temperature of 1-20 ℃ for min -1 The temperature rising speed ofHeating to 500 ℃ and 1000 ℃, and keeping the temperature for 0.5-5 h.
The lithium ion battery cathode nanofiber composite material prepared by the method also belongs to the protection scope of the invention.
The invention also provides the application of the lithium ion battery cathode nanofiber composite material in any one of the following processes, (1) preparing a battery or a battery electrode material; (2) preparing an energy storage element; (3) an electronic device is prepared.
SnO of embodiments of the invention 2 SnO in/C @ Ni nano-fiber composite material 2 the/C nanospheres are uniformly dispersed in the carbon fibers, a large number of Ni nanoparticles are dispersed on the surfaces of the fibers, the composite material fibers are mutually crosslinked to form a stable carbon skeleton matrix, a good multi-point contact network is formed, the graphitization degree of the carbon matrix is further improved due to the addition of the Ni nanoparticles, and meanwhile, the Ni also has good conductivity and provides a quick channel for electron transmission, and SnO (SnO) is a metal oxide semiconductor material 2 The gaps among the/C nanospheres are SnO 2 The volume expansion in the charging and discharging process provides space, and the carbon fiber coated on the surface is SnO 2 The volume expansion of the composite material provides buffer, and the integral stability of the composite material is ensured.
The invention has the following advantages:
SnO of the present invention 2 The preparation method of the/C @ Ni nano-fiber composite material is simple, the repeatability is high, and the SnO 2 the/C @ Ni nano-fiber composite material is prepared from SnO with the diameter of about 50nm 2 SnO self-assembled by primary nanoparticles of C and C 2 the/C nanospheres are uniformly dispersed in the carbon nanofibers, and the carbon nanofiber network provides a good conductive network and a framework support for the composite material and is SnO 2 The volume expansion of the material in the charge and discharge process provides buffer, the addition of the surface layer nano Ni particles further improves the graphitization degree of the carbon fiber, and the good conductivity of Ni obviously improves the conductivity of the composite material matrix.
SnO of the present invention 2 the/C @ Ni nano-fiber composite material as the negative electrode material of the lithium ion battery shows excellent electrochemical performance, has good electrochemical stability and rate capability, and has very high commercial applicationThe use value is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 shows the SnO prepared by hydrothermal method in the preparation method of the nano-fiber composite material of the invention 2 TEM image of/C nanosphere precursor, the SnO 2 SnO with nano-sphere precursor nano-sphere size of about 50nm 2 The secondary particles with the diameter of about 500nm are assembled by the/C primary particles;
FIG. 2 is SnO prepared by coaxial electrostatic spinning in an embodiment of the invention 2 /C @ Ni nanofiber precursor and carbonized SnO 2 SEM photograph of/C @ Ni nano-fiber composite material, wherein (a, b) is SnO 2 SEM picture of the/C @ Ni nanofiber precursor; (c, d) is SnO 2 SEM picture of/C @ Ni nanofiber composite.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Polyacrylonitrile (PAN) with the molecular weight of 150000 and polyvinylpyrrolidone (PVP) with the molecular weight of 1300000 are adopted in the embodiment of the invention, and other chemical agents are analytically pure agents and are not treated;
in the embodiment of the invention, the types of the adopted electrostatic spinning equipment are as follows: TL-Pro-BM.
Example 1 preparation of a negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K) 2 [Sn(OH) 6 ]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the potassium stannate solution, and stirring until glucose is dissolved completely to obtain a first solution.
Step two, SnO 2 Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal synthesis reaction kettle with the capacity of 100mL, placing the hydrothermal synthesis reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to prepare SnO 2 a/C nanosphere precursor. As shown in FIG. 1, is SnO 2 TEM image of/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO 2 And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate into the polyvinylpyrrolidone solution, and continuously stirring to completely dissolve the acetylacetone to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. Wherein the inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, and the advancing speed of the inner solution is 1mL h -1 The advancing speed of the external solution was 1.5mL h -1 The electrospinning voltage is 20kV, and the receiving speed of the roller is 30r min -1 The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained 2 the/C @ Ni nanofiber precursor is shown in figure 2, wherein (a and b) are SnO 2 SEM picture of/C @ Ni nanofiber precursor.
Step six, SnO 2 Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning 2 The oxidation treatment is carried out on the/C @ Ni nanofiber precursor, and the specific process is as follows:
SnO 2 Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min -1 Gradually heating to 250 ℃ at the heating speed, and keeping the temperature for 2 hours to obtain oxidized SnO 2 a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO 2 Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO 2 The carbonization treatment process of the/C @ Ni nanofiber precursor is as follows:
oxidizing SnO 2 Putting the/C @ Ni nanofiber precursor in inert gas at 5 ℃ for min -1 The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO 2 The invention relates to a/C @ Ni nanofiber composite material, in particular to a lithium ion battery cathode nanofiber composite material.
SnO is treated 2 the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The cycle performance test of the half-cell is carried out at room temperature, and the charge-discharge current density of the button half-cell is 0.1A g -1 Cycling for 200 cycles, charging and dischargingThe voltage is 0.01-1.5V; at 2.0A g -1 The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared in this example 2 the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 874mAh g under the current density -1 The coulombic efficiency is 66.2 percent, and the reversible specific capacity is 832mAh g after the circulation for 200 times -1 The capacity retention rate was 95.1%, the rate capability was 2.0A g -1 The reversible specific capacity is 348.5mAh g -1 。
Example 2 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K) 2 [Sn(OH) 6 ]) Adding the mixture into 80ml of water, performing ultrasonic treatment and stirring to completely dissolve potassium stannate, then adding 6g of glucose into the potassium stannate solution, and stirring until the glucose is completely dissolved to prepare a first solution.
Step two, SnO 2 Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal reaction kettle with the capacity of 100mL, placing the hydrothermal reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO 2 a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO 2 And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to prepare a second solution.
Step four, preparation of third solution
Adding 3.2g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.05g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h -1 The advancing speed of the external solution was 1.5mL h -1 The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm -1 The distance between an electrospinning needle head and a receiver is 18cm, the electrostatic spinning time is 10h, and SnO is obtained 2 a/C @ Ni nanofiber precursor.
Step six, SnO 2 Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning 2 The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO 2 Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO 2 the/C @ Ni nanofiber precursor.
Step seven, SnO 2 Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO 2 The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO 2 Putting the/C @ Ni nanofiber precursor in inert gas at 5 ℃ for min -1 The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO 2 The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
SnO prepared by Using this example 2 the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g -1 Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g -1 High current density ofAnd (4) carrying out a multiplying power performance test, wherein the charging and discharging voltage range is 0.01-1.5V.
SnO prepared in this example 2 the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 885mAh g under the current density -1 The coulombic efficiency is 67 percent, and the reversible specific capacity is 805mAh g after the circulation for 200 times -1 The capacity retention rate was 91.0%, and the rate capability was 2.0A g -1 The reversible specific capacity is 280mAh g -1 。
Example 3 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery negative electrode nanofiber composite material provided by the embodiment comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K) 2 [Sn(OH) 6 ]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, stirring until glucose is dissolved completely, and preparing to obtain first solution.
Step two, SnO 2 Preparation of/C nanosphere precursor
Adding the first solution with the capacity of 100mL into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO 2 a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 4g of SnO 2 And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to prepare a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 3g of nickel acetylacetonate, and continuously stirring to completely dissolve the nickel acetylacetonate to prepare a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 0.1mL h -1 The advancing speed of the external solution was 0.15mL h -1 The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm -1 The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained 2 a/C @ Ni nanofiber precursor.
Step six, SnO 2 Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning 2 The oxidation treatment process of the/C @ Ni nanofiber precursor is as follows:
SnO 2 putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO 2 a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO 2 Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO 2 The carbonization treatment process of the/C @ Ni nanofiber precursor is as follows:
oxidizing SnO 2 The precursor of the/C @ Ni nano-fiber is put in inert gas at 5 ℃ for min -1 The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO 2 The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO 2 the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g -1 Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g -1 The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared by the invention 2 the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 725mAh g under the current density -1 The coulombic efficiency is 69 percent, and the reversible specific capacity after 200 times of circulation is 696mAh g -1 The capacity retention rate was 96%, and the rate capability was 2.0A g -1 The reversible specific capacity is 294mAh g -1 。
Example 4 preparation of negative electrode nanofiber composite for lithium ion batteries
The preparation method of the lithium ion battery cathode nanofiber composite material provided by the embodiment of the invention comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K) 2 [Sn(OH) 6 ]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, and stirring until glucose is dissolved completely to obtain first solution.
Step two, SnO 2 Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal reaction kettle with the capacity of 100mL, placing the hydrothermal reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to obtain SnO 2 a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 2g of SnO 2 And continuously stirring the/C nanosphere precursor to uniformly disperse the precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to obtain a third solution.
Step five, coaxial electrostatic spinning
In this step, the types of the electrostatic spinning equipment adopted are: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h -1 The advancing speed of the external solution was 1.5mL h -1 The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm -1 The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained 2 a/C @ Ni nanofiber precursor.
Step six, SnO 2 Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning 2 The oxidation treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
SnO is treated 2 Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO 2 a/C @ Ni nanofiber precursor.
Step seven, oxidized SnO 2 Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO 2 The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO 2 Putting the/C @ Ni nanofiber precursor in inert gas at 5 ℃ for min -1 The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO 2 The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO 2 the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g -1 Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g -1 The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO prepared by the invention 2 Use of/C @ Ni nano fiber composite material as lithium ion batteryThe negative electrode material is tested, and the test result is as follows: at 0.1A g -1 The reversible specific capacity of the first loop is 496mAh g under the current density -1 The coulombic efficiency is 72 percent, and the reversible specific capacity after 200 times of circulation is 481mAh g -1 The capacity retention rate is 97%, and the rate capability is that the current density is 2.0A g -1 The reversible specific capacity is 363mAh g -1 。
Example 5 lithium ion battery negative electrode nanofiber composite and electrochemical performance test
The preparation method of the lithium ion battery cathode nanofiber composite material of the embodiment specifically comprises the following steps:
step one, preparation of a first solution
3.5g of potassium stannate (K) 2 [Sn(OH) 6 ]) Adding into 80ml water, ultrasonic treating, stirring to dissolve potassium stannate completely, adding 6g glucose into the above solution, and stirring until glucose is dissolved completely to obtain first solution.
Step two, SnO 2 Preparation of/C nanosphere precursor
Adding the first solution into a hydrothermal reaction kettle with the capacity of 100mL, placing the hydrothermal reaction kettle in an explosion-proof hydrothermal oven at 180 ℃, preserving heat for 4 hours, cooling, cleaning, centrifuging and drying a reaction product to prepare SnO 2 a/C nanosphere precursor.
Step three, preparation of second solution
Adding 1.8g of polyacrylonitrile into 20ml of N, N-dimethylformamide, heating and stirring at 80 ℃ until the polyacrylonitrile is completely dissolved, and then adding 9g of SnO 2 And C, continuously stirring the nanosphere precursor to uniformly disperse the nanosphere precursor to obtain a second solution.
Step four, preparation of third solution
Adding 3g of polyvinylpyrrolidone into 20ml of N, N-dimethylformamide, heating and stirring at 60 ℃ until the polyvinylpyrrolidone is completely dissolved, then adding 0.8g of nickel acetylacetonate, and continuing stirring to completely dissolve the nickel acetylacetonate to obtain a third solution.
Step five, coaxial electrostatic spinning
In this step, the electrostatic spinning equipment is usedThe model is as follows: TL-Pro-BM. The inner solution of the coaxial electrostatic spinning is a second solution, the outer solution is a third solution, wherein the advancing speed of the inner solution is 1mL h -1 The advancing speed of the external solution was 1.5mL h -1 The electrospinning voltage is 20kV, and the receiving speed of the roller is 30 rpm -1 The distance between the electrospinning needle head and the receiver is 18cm, the electrospinning time is 10h, and SnO is obtained 2 the/C @ Ni nanofiber precursor.
Step six, SnO 2 Oxidation treatment of/C @ Ni nanofiber precursor
SnO prepared by coaxial electrostatic spinning 2 The oxidation treatment process of the/C @ Ni nanofiber precursor is as follows:
SnO 2 Putting the/C @ Ni nanofiber precursor in air at 10 ℃ for min -1 The temperature rising speed is gradually increased to 250 ℃, and the temperature is kept constant for 2 hours to obtain oxidized SnO 2 the/C @ Ni nanofiber precursor.
Step seven, oxidized SnO 2 Carbonization treatment of/C @ Ni nanofiber precursor
For oxidized SnO 2 The carbonization treatment process of the/C @ Ni nanofiber precursor comprises the following steps:
oxidizing SnO 2 The precursor of the/C @ Ni nano-fiber is put in inert gas at 5 ℃ for min -1 The temperature is gradually increased to 600 ℃ at the temperature rising speed, and the temperature is kept for 3 hours to obtain SnO 2 The invention relates to a/C @ Ni nano-fiber composite material, in particular to a lithium ion battery cathode nano-fiber composite material.
The prepared SnO 2 the/C @ Ni nano-fiber composite material is assembled into a 2032 type button half cell in a glove box in a high-purity argon atmosphere. The half-cell is subjected to cycle performance test at room temperature, and the charge-discharge current density is 0.1A g -1 Circulating for 200 circles, wherein the charging and discharging voltage is 0.01-1.5V; at 2.0A g -1 The multiplying power performance test is carried out under the high current density, and the charging and discharging voltage range is 0.01-1.5V.
SnO of the present invention 2 the/C @ Ni nano-fiber composite material is used as a lithium ion battery negative electrode material for testing, and the test result is as follows: at 0.1A g -1 At a current density, the first turn canThe inverse specific capacity is 997mAh g -1 The coulombic efficiency is 52 percent, and the reversible specific capacity is 561mAh g after circulation for 200 times -1 The capacity retention rate is 56%, and the rate capability is that the current density is 2.0A g -1 The reversible specific capacity is 354mAh g -1 。
Comparative example
In this comparative example, the difference from example 1 is that: at SnO 2 In the preparation process of the/C nanofiber composite material, nickel acetylacetonate is not added in the process of preparing the third solution, and the rest is the same as that of the embodiment 1.
SnO prepared by this comparison 2 the/C nano-fiber composite material is used as the negative electrode material of the lithium ion battery to be tested and is 0.1A g -1 The reversible specific capacity of the first loop is 906mAh g under the current density -1 The coulombic efficiency is 65 percent, and the reversible specific capacity after 200 times of circulation is 796mAh g -1 The capacity retention rate was 87.8%, the rate capability was 2.0A g -1 The reversible specific capacity is 256mAh g -1 。
The comparison between examples 1-3 and comparative example 1 shows that Ni nanoparticles have good promotion effect on the rate performance improvement of the composite material, and the results of examples 4-5 show that SnO is 2 The capacitance of the material can be effectively improved.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements may be made based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A preparation method of a negative electrode nano-fiber composite material of a lithium ion battery is characterized in that,
the preparation method comprises the following steps: using a catalyst containing SnO 2 Preparing SnO (SnO) from second solution of/C nanosphere precursor and third solution containing nickel acetylacetonate through coaxial electrostatic spinning 2 a/C @ Ni nanofiber precursor;
the SnO 2 SnO is obtained by oxidizing and carbonizing a/C @ Ni nanofiber precursor 2 the/C @ Ni nano-fiber composite material is the lithium ion battery negative electrode nano-fiber composite material;
the SnO 2 The preparation method of the/C nanosphere precursor comprises the following steps:
adding potassium stannate into water, stirring and carrying out ultrasonic treatment until the potassium stannate is completely dissolved to obtain a potassium stannate solution, adding glucose, stirring until the potassium stannate is completely dissolved to obtain a first solution, adding the first solution into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an explosion-proof oven, washing, centrifuging and drying a reaction product to obtain the SnO 2 a/C nanosphere precursor;
wherein, in the first solution, the mass fraction of the potassium stannate is 1-10%, and the mass ratio of the glucose to the potassium stannate is 0.5-10;
the preparation method of the second solution comprises the following steps:
adding Polyacrylonitrile (PAN) into N, N-Dimethylformamide (DMF), stirring at 80 deg.C for 30min to dissolve completely, adding the SnO 2 the/C nanosphere precursor is stirred for 30min to obtain the second solution;
in the second solution, the mass fraction of polyacrylonitrile is 1% -30%, and the SnO 2 The mass ratio of the/C nanosphere precursor to the polyacrylonitrile is 0.1-5;
the preparation method of the third solution comprises the following steps:
adding polyvinylpyrrolidone (PVP) into N, N-Dimethylformamide (DMF), stirring at 60 deg.C for 30min until PVP is completely dissolved, adding nickel acetylacetonate, and stirring for 30min to obtain a third solution;
wherein, in the third solution, the PVP accounts for 10-30% by mass; the mass ratio of the nickel acetylacetonate to the PVP is 0.01-5.
2. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the coaxial electrostatic spinning conditions are as follows:
the inner layer of pipeline is filled with the second solution, and the outer layer of pipeline is filled with the second solutionThe third solution has voltage of 5-50kV and roller receiving speed of 0-100r min -1 Push-injection pushing speed of 0.1-10mL h -1 The distance between the electrospinning needle head and the receiver is 5-30cm, and the electrospinning time is 1-100 h.
3. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the oxidation treatment process comprises the following steps:
the SnO 2 The precursor of the/C @ Ni nano-fiber is put in the air at the temperature of 1-10 ℃ for min -1 The temperature rising speed is gradually increased to 150-300 ℃, and the temperature is kept for 0.5-3 h.
4. The method for preparing the negative nanofiber composite for lithium ion batteries according to claim 1,
the carbonization treatment process comprises the following steps:
oxidation treated SnO 2 The precursor of the/C @ Ni nano-fiber is put in inert gas at the temperature of 1-20 ℃ for min -1 The temperature rising speed is gradually raised to 500-1000 ℃, and the temperature is kept for 0.5-5 h.
5. The lithium ion battery negative electrode nanofiber composite prepared by the method of any one of claims 1 to 4.
6. The use of the lithium ion battery negative electrode nanofiber composite of claim 5 in the preparation of a battery or battery electrode material.
7. Use of the lithium ion battery negative electrode nanofiber composite of claim 5 in the preparation of an energy storage element.
8. The use of the lithium ion battery negative electrode nanofiber composite of claim 5 in the preparation of electronic devices.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022518A (en) * | 1996-09-24 | 2000-02-08 | Petoca, Ltd. | Surface graphitized carbon material and process for producing the same |
| CN103972480A (en) * | 2014-03-26 | 2014-08-06 | 北京理工大学 | Preparation method of carbon fiber/sulfur composite positive material with multilevel structure |
| CN105155002A (en) * | 2015-07-09 | 2015-12-16 | 长春理工大学 | Nanometer cable with three functions of conduction, magnetism and absorption and preparation method for same |
| CN105148892A (en) * | 2015-08-24 | 2015-12-16 | 中国人民解放军国防科学技术大学 | Graphene/carbon nano tube/carbon nanofiber electrocatalyst and preparation method thereof |
| CN109888215A (en) * | 2019-02-19 | 2019-06-14 | 福建翔丰华新能源材料有限公司 | A method of nucleocapsid structure lithium ion battery negative electrode material is prepared with electrostatic spinning |
| CN111115618A (en) * | 2019-12-02 | 2020-05-08 | 深圳石墨烯创新中心有限公司 | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013130690A1 (en) * | 2012-03-02 | 2013-09-06 | Cornell University | Lithium ion batteries comprising nanofibers |
| CN102629679B (en) * | 2012-04-28 | 2018-04-20 | 中国科学院理化技术研究所 | Nanofiber lithium ion battery separator material with composite construction and preparation method thereof |
| EP3254321A4 (en) * | 2015-02-04 | 2018-07-18 | Axium IP, LLC | Silicon-carbon nanostructured composites |
| CN110656442B (en) * | 2019-08-20 | 2021-01-15 | 苏州大学 | Lithium ion battery diaphragm and preparation method thereof |
-
2020
- 2020-11-23 CN CN202011324288.XA patent/CN112563468B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6022518A (en) * | 1996-09-24 | 2000-02-08 | Petoca, Ltd. | Surface graphitized carbon material and process for producing the same |
| CN103972480A (en) * | 2014-03-26 | 2014-08-06 | 北京理工大学 | Preparation method of carbon fiber/sulfur composite positive material with multilevel structure |
| CN105155002A (en) * | 2015-07-09 | 2015-12-16 | 长春理工大学 | Nanometer cable with three functions of conduction, magnetism and absorption and preparation method for same |
| CN105148892A (en) * | 2015-08-24 | 2015-12-16 | 中国人民解放军国防科学技术大学 | Graphene/carbon nano tube/carbon nanofiber electrocatalyst and preparation method thereof |
| CN109888215A (en) * | 2019-02-19 | 2019-06-14 | 福建翔丰华新能源材料有限公司 | A method of nucleocapsid structure lithium ion battery negative electrode material is prepared with electrostatic spinning |
| CN111115618A (en) * | 2019-12-02 | 2020-05-08 | 深圳石墨烯创新中心有限公司 | Graphene/carbon/tin oxide nano composite material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Electrospun free-standing N-doped C@SnO2 anode paper for flexible Li-ion batteries;Xing Liu et a;《Materials Research Bulletin》;20180915;第109卷;第41页左栏第1段，第42页左栏第2段 * |
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