CN108807912A - A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C - Google Patents

A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C Download PDF

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CN108807912A
CN108807912A CN201810609576.6A CN201810609576A CN108807912A CN 108807912 A CN108807912 A CN 108807912A CN 201810609576 A CN201810609576 A CN 201810609576A CN 108807912 A CN108807912 A CN 108807912A
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CN108807912B (en
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锁国权
李丹
杨艳玲
王祎
左玉
侯小江
冯雷
王成威
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Shenzhen Wanzhida Technology Co ltd
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of C@SnOX (x=0,1,2)The 3- amino-phenols of certain mass are dissolved in deionized water and obtain solution A by the preparation and application of the mesoporous shape hollow nano spherical structures of@C；Formaldehyde is added into above-mentioned solution A and obtains solution B；Into above-mentioned solution B, addition acetone obtains solution or emulsion C obtains forerunner's hollow nanosphere；Above-mentioned forerunner's hollow nanosphere is placed in deionized water and obtains solution D；Organic matter is added and obtains solution E；The stannous chloride that certain mass is added in solution E obtains solution F；The urea that certain mass is added in solution F obtains solution G；Above-mentioned solution G is transferred to hydrothermal reaction kettle, carries out hydro-thermal reaction, cooling, centrifugation, drying obtain composite Nano hollow ball；By obtained hollow nanosphere in certain temperature, it is carbonized in the gaseous mixture of argon gas and hydrogen, obtains C@SnOX (x=0,1,2)The mesoporous shape hollow nanosphere of@C, the raw materials used in the present invention is cheap, and preparation manipulation is simple.

Description

A kind of C@SnOx(x=0,1,2)The preparation and application of the mesoporous shape hollow nano spherical structures of@C
Technical field
The present invention relates to power battery material technical field, more particularly to a kind of C@SnOX (x=0,1,2)In the mesoporous shape nanometers of@C The preparation and application of empty spherical structure.
Background technology
Energy crisis is the important issue for influencing sustainable economic development all the time with problem of environmental pollution.Therefore it finds The new energy becomes urgent problem to be solved, and secondary power battery enters our visual field at this time.It is close for the high energy of acquisition Degree, becomes the first choice of current secondary cell, extremely negative normal electrode positioned at the upper left lithium metal of the periodic table of elements After current potential (- 3.04V) means that it forms full battery with anode, battery has high voltage output；And lithium metal is most light Metal, this further means that with higher specific capacity.Energy=specific capacity × voltage, therefore lithium associated batteries Technology Energy density It is almost highest in existing battery.In addition, lithium ion battery also possesses small advantage.Therefore its production in the nineties The revolutionary development of the numerous areas such as smart mobile phone, camera, laptop and electric vehicle is advanced after industry rapidly.But The content of lithium only takes up an area the 0.017% of shell total content, and as the amount used increases, lithium is again insufficient, and the price of lithium is higher and higher, and The sodium of same main group and the content of potassium are respectively 2.09% and 2.36%, and price is more much lower than lithium.In addition lithium battery develops to existing Seeming to encounter one " bottleneck period ", energy density Slow lifting, cost declines not rapid and warm in fast charge, adaptation Challenge has all been encountered in terms of degree range, more large scale deployment application (electric vehicle, energy storage) and resource abundance.Because of this person Always search for the deficiency that a kind of new secondary cell technology makes up lithium electricity, kalium ion battery is of concern.
The research of kalium ion battery is scarcely out of swaddling-clothes, and is the hot spot of research, and relevant report also increases year by year.Potassium ion Radius (0.98) is more than lithium ion radius (0.69) so that the potential barrier overcome needed for potassium ion diffusion in charge and discharge process is more Greatly, to make diffusion rate substantially reduce.And the negative material graphite layers being commercialized are away from too small, improper deintercalation potassium from Son, therefore need to find suitable battery cathode storage potassium material.Stannic oxide is a kind of important lithium ion battery negative material, it With higher theoretical capacity (783Amhg-1), it is more than 2 times of carbon negative pole material theoretical capacity of commercialization, compared to other oxygen Compound semi-conducting material have high conductivity (about 21.1 Ω cm) and compared with high electron mobility (about 100~ 200cm2·V-1·S-1), but its volume expansion in charge and discharge process can reach original 3 times, be easy to powdered or Person reunites so that the cycle performance of the kalium ion battery of composition is relatively poor.Therefore the cladding that carbon is carried out on its surface, utilizes carbon Alleviate SnO in the space that ball providesX (X=0,1,2)Volume expansion, also improve the electric conductivity of composite material in addition, be conducive to potassium Ion is quickly embedded and deviates from, and also improves circulating battery stability, extends battery life.This is in power kalium ion battery There is prodigious potential using value in negative material.The material has nontoxic simultaneously, pollution-free, and security performance is high, raw material The advantages that extensive.Mesoporous shape hollow nano spherical structure SnOX (X=0,1,2)With quantum size effect, big specific surface area, high surface Activity, mesoporous shape hollow nano spherical structure SnOX (X=0,1,2)Material has extensively in the numerous areas such as energy conversion and energy storage devices General application prospect, therefore as the hot spot of research.
C@SnOX (x=0,1,2)@C kalium ion battery negative electrode active materials, preparation method and correlative study work are current also not It appears in the newspapers.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of C@SnOX (x=0,1,2)@C are situated between The preparation and application of poroid hollow nano spherical structure select a kind of hot method of templating solvent to make the mesoporous spherical knot of shape hollow nano Structure, adjusts reaction temperature and the time obtains cheap kalium ion battery negative material.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of C@SnOX (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, includes the following steps：
1), the 3- amino-phenols of certain mass are dissolved in deionized water and obtain solution A；
2) formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution or emulsion C, are stirred into certain time, is dried at a certain temperature after centrifugation, is obtained forerunner and receive Rice hollow ball；
5), above-mentioned forerunner's hollow nanosphere is placed in 30ml deionized waters, ultrasonic certain time obtains solution D；
6) organic matter, under magnetic stirring, is added in solution D, obtains solution E；
7) stannous chloride of certain mass, under magnetic stirring, is added in solution E, obtains solution F；
8) urea of certain mass, under magnetic stirring, is added in solution F, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction is carried out, cools down after reaction, centrifuges a constant temperature The lower drying of degree, obtains composite Nano hollow ball；
10) it, by obtained hollow nanosphere in certain temperature, is carbonized in the gaseous mixture of argon gas and hydrogen, obtains C@ SnOX (x=0,1,2)The mesoporous shape hollow nanosphere of@C.
In the step 2), the mass ratio of 3- amino-phenols and formaldehyde is 1~10:4~9.
In the step 3), the mass ratio of 3- amino-phenols and acetone is 1~10:3~16.
In the step 4), mixing time 6-24h, the rotating speed of centrifugation and time be respectively 8000rpm/min~ 10000rpm/min, 10min, drying temperature are 60 DEG C, 8h.
In the step 5), the ultrasonic time is 10min~60min.
In the step 6), organic matter is glucose, dopamine, sodium citrate and beta-cyclodextrin etc., wherein 3- aminobenzenes Phenol and organic matter and mass ratio be：1~10:10~90.
In the step 7), the mass ratio of 3- amino-phenols and stannous chloride is：1~10:6.
In the step 8), the mass ratio of 3- amino-phenols and urea is：1~10:6.
In the step 9), the condition of hydro-thermal reaction is 180 DEG C~200 DEG C, 18h~for 24 hours；The condition of centrifugation is 8000rmp/min~10000rmp/min, 10min, dry condition are 60 DEG C, for 24 hours.
In the step 10), the temperature of carbonization is 450 DEG C~650 DEG C, and the ratio of argon gas and hydrogen is 1：2~2： 1.
C@SnOX (x=0,1,2)The mesoporous shape hollow nano spherical structures of@C are applied to the preparation of kalium ion battery, including following step Suddenly；
1), weighing mass ratio respectively is：9-Y:1:The C@SnO of Y (1≤Y≤2)X (x=0,1,2)@C composites, carbon black and poly- Vinylidene, wherein by Kynoar wiring solution-forming, step is that Kynoar is added to N-Methyl pyrrolidone, is made into matter The solution that score is 4% is measured, 12h is stirred, is in weak yellow liquid, that is, Kynoar solution is made into, then by Kynoar Solution and carbon black and C@SnOX (x=0,1,2)@C composites mix in the agate mortar, grind 1~3h, are then uniformly coated in In copper foil current collector；Dry 6h, the disk of 8mm is cut into mold, the dry 12h of 60 DEG C of vacuum is then placed in gloves at 60 DEG C Prepare packed battery in case；
2) it is to electrode with metallic potassium, electrolyte is the ethylene carbonate of 1M Potassium Hexafluorophosphates, in the environment of high-purity argon gas (volume ratio of EC and DMC are 1 to the solution of ester (EC) and carbonic acid dioctyl phthalate (DMC)：1), microporous polypropylene membrane is battery diaphragm, group Dress is button cell；Last button type battery carries out constant current charge-discharge capacity and cycle performance test.
Beneficial effects of the present invention：
C@SnO have been prepared using above-mentioned stepsX (x=0,1,2)The mesoporous shape nanospheres of@C, raw material used is cheap, prepares letter Just, easy to operation.The purity of material is relatively high, and the uniform particle sizes of Mesoporous Spheres are easy to industrialize.Meanwhile by C@ SnOX (x=0,1,2)The mesoporous shape hollow nanospheres of@C show excellent chemical property as the negative material of potassium ion, overcome Powdered caused by volume expansion of the tin oxide in charge and discharge, while there is high specific capacity again, be conducive to develop potassium from Sub- battery.
Raw materials used cheap, preparation manipulation is simple, and the purity of obtained material is high, and the particle size of Mesoporous Spheres is uniform, is situated between Pore size distribution is uniform, it is easy to accomplish industrialization；Excellent chemical property is shown as the negative material of kalium ion battery.
Description of the drawings
Fig. 1 is that the SEM of presoma phenolic resin ball of the present invention schemes.
Fig. 2 is the SEM figures of the present invention.
Fig. 3 is charge and discharge cycles figure of the present invention as kalium ion battery negative material.
Specific implementation mode
With reference to embodiment, invention is further described in detail.
Embodiment 1
A kind of C@SnOX (x=0,1,2)The preparation method of the mesoporous shape hollow nano spherical structures of@C and application, include the following steps：
1), the 3- amino-phenols of 0.01g are dissolved in 30mL deionized waters and obtain solution A；
2) 0.05ml formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) 5ml acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution C, is stirred into 6h, 8h is dried in 60 DEG C of baking ovens after 8000rpm/min, 10min centrifugation, obtains forerunner Nanosphere；
5), above-mentioned forerunner's nanosphere is placed in 30ml deionized waters, ultrasonic 60min obtains solution D；
6) glucose 0.3g, under magnetic stirring, is added, obtains solution E；
7) stannous chloride of 0.564g, under magnetic stirring, is added, obtains solution F；
8) urea of 0.6g, under magnetic stirring, is added, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction 18h is carried out at 180 DEG C.It cools down after reaction, 8000rpm/min, 10min are centrifuged, and are dried for 24 hours at 60 DEG C, are obtained compound hollow nanospheres；
10), by obtained compound nano-hollow sphere at 450 DEG C, argon gas is with hydrogen flow rate ratio：1:It is carried out under conditions of 2 Carbonization, obtains C@SnOX (x=0,1,2)The mesoporous shape nano-hollow ball of@C.
Embodiment 2
A kind of C@SnOX (x=0,1,2)The preparation method of the mesoporous shape hollow nanospheres structures of@C and application, include the following steps：
1), the 3- amino-phenols of 0.05g are dissolved in 30mL deionized waters and obtain solution A；
2) 0.05ml formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) 10ml acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution C, is stirred into 6h, 8h is dried in 60 DEG C of baking ovens after 8000rpm/min, 10min centrifugation, obtains forerunner Hollow nanospheres；
5), above-mentioned forerunner's hollow nanospheres are placed in 30ml deionized waters, ultrasonic 60min obtains solution D；
6) glucose 0.6g, under magnetic stirring, is added, obtains solution E；
7) stannous chloride of 0.564g, under magnetic stirring, is added, obtains solution F；
8) urea of 0.6g, under magnetic stirring, is added, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction 18h is carried out at 180 DEG C.It cools down after reaction, 8000rpm/min, 10min are centrifuged, and are dried for 24 hours at 60 DEG C, are obtained compound hollow nanospheres；
10), by obtained compound nano-hollow sphere at 500 DEG C, argon gas is with hydrogen flow rate ratio：1:It is carried out under conditions of 2 Carbonization, obtains C@SnOX (x=0,1,2)The mesoporous shape nano-hollow ball of@C.
Embodiment 3
A kind of C@SnOX (x=0,1,2)The preparation method of the mesoporous shape hollow nanospheres structures of@C and application, include the following steps：
1), the 3- amino-phenols of 0.05g are dissolved in 30mL deionized waters and obtain solution A；
2) 0.1ml formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) 15ml acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution C, is stirred into 6h, 8h is dried in 60 DEG C of baking ovens after 8000rpm/min, 10min centrifugation, obtains forerunner Hollow nanospheres；
5), above-mentioned forerunner's hollow nanospheres are placed in 30ml deionized waters, ultrasonic 60min obtains solution D；
6) glucose 0.6g, under magnetic stirring, is added, obtains solution E；
7) stannous chloride of 0.564g, under magnetic stirring, is added, obtains solution F；
8) urea of 0.6g, under magnetic stirring, is added, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction 18h is carried out at 180 DEG C.It cools down after reaction, 8000rpm/min, 10min are centrifuged, and are dried for 24 hours at 60 DEG C, are obtained compound hollow nanospheres；
10), by obtained compound nano-hollow sphere at 550 DEG C, argon gas is with hydrogen flow rate ratio：1:It is carried out under conditions of 2 Carbonization, obtains C@SnOX (x=0,1,2)The mesoporous shape nano-hollow ball of@C.
Embodiment 4
A kind of C@SnOX (x=0,1,2)The preparation method of the mesoporous shape hollow nanospheres structures of@C and application, include the following steps：
1), the 3- amino-phenols of 0.05g are dissolved in 30mL deionized waters and obtain solution A；
2) 0.1ml formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) 20ml acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution C, is stirred into 6h, 8h is dried in 60 DEG C of baking ovens after 8000rpm/min, 10min centrifugation, obtains forerunner Hollow nanospheres；
5), above-mentioned forerunner's hollow nanospheres are placed in 30ml deionized waters, ultrasonic 60min obtains solution D；
6) glucose 0.9g, under magnetic stirring, is added, obtains solution E；
7) stannous chloride of 0.564g, under magnetic stirring, is added, obtains solution F；
8) urea of 0.6g, under magnetic stirring, is added, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction 18h is carried out at 180 DEG C.It cools down after reaction, 8000rpm/min, 10min are centrifuged, and are dried for 24 hours at 60 DEG C, are obtained compound hollow nanospheres；
10), by obtained compound nano-hollow sphere at 600 DEG C, argon gas is with hydrogen flow rate ratio：1:It is carried out under conditions of 1 Carbonization, obtains C@SnOX (x=0,1,2)The mesoporous shape nano-hollow ball of@C.
Embodiment 5
A kind of C@SnOX (x=0,1,2)The preparation method of the mesoporous shape hollow nanospheres structures of@C and application, include the following steps：
1), the 3- amino-phenols of 0.1g are dissolved in 30mL deionized waters and obtain solution A；
2) 0.1ml formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) 20ml acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution C, is stirred into 6h, 8h is dried in 60 DEG C of baking ovens after 8000rpm/min, 10min centrifugation, obtains forerunner Hollow nanospheres；
5), above-mentioned forerunner's hollow nanospheres are placed in 30ml deionized waters, ultrasonic 60min obtains solution D；
6) glucose 0.9g, under magnetic stirring, is added, obtains solution E；
7) stannous chloride of 0.564g, under magnetic stirring, is added, obtains solution F；
8) urea of 0.6g, under magnetic stirring, is added, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction 18h is carried out at 180 DEG C.It cools down after reaction, 8000rpm/min, 10min are centrifuged, and are dried for 24 hours at 60 DEG C, are obtained compound hollow nanospheres；
10), by obtained compound nano-hollow sphere at 650 DEG C, argon gas is with hydrogen flow rate ratio：1:It is carried out under conditions of 1 Carbonization, obtains C@SnOX (x=0,1,2)The mesoporous shape nano-hollow ball of@C.
As shown in Figure 1, being that 12h is mixed in 3- amino-phenols and formaldehyde, centrifuge, the obtained presoma after drying.? The pattern of grain is the presoma of the smooth carbon ball on surface, and for the radius of sphere in 400nm or so, sphere is uniform.
It is that the C@SnO obtained after stannic chloride and glucose, then high temperature cabonization are added as shown in Figure 2X (x=0,1,2)@C's is mesoporous Shape carbon ball, there are many small holes for spherome surface, are to be passed through hydrogen in carbonisation to have corrasion to be formed sphere.Sphere The hole of surface etch is uniform, of the same size.The radius size of mesoporous sphere is about 500nm.
As shown in figure 3, being C@SnOX (x=0,1,2)@C are 50mA/g in current density, and voltage is the 1st time of 0.01-2.6V, 2nd time, the 5th, the 10th constant current charge-discharge cyclic curve figure.Discharge capacity reaches 372.8mAh/g for the first time as seen from Figure 3, fills Electricity is 121.1mAh/g, and coulombic efficiency 32.48%, the relatively low reason of specific capacity may be the shape in charge and discharge process for the first time At SEI films, the potassium ion in partial electrolyte liquid is consumed.Coulombic efficiency in the 2nd, 5,10 time is respectively 36.36%, 44.34%, 48.01%, coulombic efficiency is gradually increasing, and illustrates C@SnOX (x=0,1,2)The cycle performance of@C-materials is preferable, utilizes Carbon coating alleviates the volume expansion of Sn and SnO2A in charge and discharge process so that the cycle life of material increases.

Claims (10)

1. a kind of C@SnOX (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, which is characterized in that include the following steps：
1), the 3- amino-phenols of certain mass are dissolved in deionized water and obtain solution A；
2) formaldehyde, under magnetic stirring, is added into above-mentioned solution A and obtains solution B；
3) acetone, under magnetic stirring, is added into above-mentioned solution B and obtains solution or emulsion C；
4) above-mentioned solution or emulsion C, are stirred into certain time, dried at a certain temperature after centrifugation, is obtained in forerunner's nanometer Empty ball；
5), above-mentioned forerunner's hollow nanosphere is placed in 30ml deionized waters, ultrasonic certain time obtains solution D；
6) organic matter, under magnetic stirring, is added in solution D, obtains solution E；
7) stannous chloride of certain mass, under magnetic stirring, is added in solution E, obtains solution F；
8) urea of certain mass, under magnetic stirring, is added in solution F, obtains solution G；
9) above-mentioned solution G, is transferred to hydrothermal reaction kettle, hydro-thermal reaction is carried out, cools down after reaction, is centrifuged under certain temperature It is dry, obtain composite Nano hollow ball；
10) it, by obtained hollow nanosphere in certain temperature, is carbonized in the gaseous mixture of argon gas and hydrogen, obtains C@ SnOX (x=0,1,2)The mesoporous shape hollow nanosphere of@C.
2. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 2), the mass ratio of 3- amino-phenols and formaldehyde is 1~10:4~9.
3. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 3), the mass ratio of 3- amino-phenols and acetone is 1~10:3~16.
4. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature Be, in the step 4), mixing time 6-24h, the rotating speed of centrifugation and time be respectively 8000rpm/min~ 10000rpm/min, 10min, drying temperature are 60 DEG C, 8h.
5. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 5), the ultrasonic time is 10min~60min.
6. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature Be, in the step 6), organic matter is glucose, dopamine, sodium citrate and beta-cyclodextrin etc., wherein 3- amino-phenols with Organic matter and mass ratio be：1~10:10~90.
7. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 7), the mass ratio of 3- amino-phenols and stannous chloride is：1~10:6；
In the step 8), the mass ratio of 3- amino-phenols and urea is：1~10:6.
8. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 9), the condition of hydro-thermal reaction is 180 DEG C~200 DEG C, 18h~for 24 hours；The condition of centrifugation is 8000rmp/ Min~10000rmp/min, 10min, dry condition are 60 DEG C, for 24 hours.
9. a kind of C@SnO according to claim 1X (x=0,1,2)The preparation of the mesoporous shape hollow nano spherical structures of@C, feature It is, in the step 10), the temperature of carbonization is 450 DEG C~650 DEG C, and the ratio of argon gas and hydrogen is 1：2~2：1.
10. based on C@SnO described in claim 1X (x=0,1,2)The mesoporous shape hollow nano spherical structures of@C are applied to kalium ion battery It prepares, which is characterized in that include the following steps；
1), weighing mass ratio respectively is：9-Y:1:The C@SnO of YX (x=0,1,2)@C composites, carbon black and Kynoar, wherein By Kynoar wiring solution-forming, step is that Kynoar is added to N-Methyl pyrrolidone, and it is 4% to be made into mass fraction Solution stirs 12h, is in weak yellow liquid, that is, Kynoar solution is made into, then by Kynoar solution and carbon black and C@ SnOX (x=0,1,2)@C composites mix in the agate mortar, grind 1~3h, are then uniformly coated in copper foil current collector； The dry 6h at 60 DEG C, the disk of 8mm is cut into mold, and the dry 12h of 60 DEG C of vacuum is then placed in glove box and prepares dress electricity Pond；
2) it is to electrode with metallic potassium, electrolyte is the ethylene carbonate of 1M Potassium Hexafluorophosphates, in the environment of high-purity argon gas (EC) (volume ratio of EC and DMC are 1 with the solution of carbonic acid dioctyl phthalate (DMC)：1), microporous polypropylene membrane is battery diaphragm, assembling For button cell；Last button type battery carries out constant current charge-discharge capacity and cycle performance test.
CN201810609576.6A 2018-06-13 2018-06-13 C @ SnOx(x=0,1,2)Preparation and application of @ C mesoporous nano hollow sphere structure Active CN108807912B (en)

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CN110697762A (en) * 2019-10-15 2020-01-17 哈尔滨工业大学 Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material
CN112357956A (en) * 2020-09-28 2021-02-12 浙江理工大学 Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof
CN115347173A (en) * 2022-08-30 2022-11-15 陕西科技大学 Three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material and preparation method and application thereof

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CN109817934A (en) * 2019-01-30 2019-05-28 陕西科技大学 A kind of hydro-thermal calcination method preparation carbon coating Sn/SnO2The method of/carbon cloth negative electrode material
CN110697762A (en) * 2019-10-15 2020-01-17 哈尔滨工业大学 Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material
CN110697762B (en) * 2019-10-15 2022-03-29 哈尔滨工业大学 Hollow structure Sn/SnO2Preparation method of @ C lithium ion battery negative electrode material
CN112357956A (en) * 2020-09-28 2021-02-12 浙江理工大学 Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof
CN115347173A (en) * 2022-08-30 2022-11-15 陕西科技大学 Three-dimensional bridged double-carbon-limited-domain tin oxide-based negative electrode material and preparation method and application thereof

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