CN108039472A - A kind of preparation method and application of the hollow micron cube composite material of carbon coating zinc metastannate - Google Patents

A kind of preparation method and application of the hollow micron cube composite material of carbon coating zinc metastannate Download PDF

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CN108039472A
CN108039472A CN201711315812.5A CN201711315812A CN108039472A CN 108039472 A CN108039472 A CN 108039472A CN 201711315812 A CN201711315812 A CN 201711315812A CN 108039472 A CN108039472 A CN 108039472A
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hollow
carbon coating
composite material
micron cube
deionized water
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王刚
王惠
马菁瑶
王贝贝
王佳妹
白晋涛
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Northwest University
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Northwest University
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

A kind of preparation method and application of the hollow micron cube composite material of carbon coating zinc metastannate, it is related to a kind of preparation method of composite material.The invention aims to solve existing ZnSnO3The problem of specific capacity is low and high rate performance is poor.Method：First, solution is prepared；2nd, reaction solution is prepared；3rd, hollow ZnSn (OH) is prepared6White powder；4th, hollow ZnSnO is prepared3Micron cube；5th, hydro-thermal reaction；6th, calcine, obtain the hollow micron cube composite material of carbon coating zinc metastannate.A kind of hollow micron cube composite material conduct of carbon coating zinc metastannate prepares lithium ion battery negative material or is used as anode material of lithium-ion battery application.The present invention can obtain a kind of hollow micron cube composite material of carbon coating zinc metastannate.

Description

A kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate and Using
Technical field
The present invention relates to a kind of preparation method of composite material.
Background technology
Rechargeable lithium ion batteries are portable due to being widely used in large capacity, long-life and advantages of environment protection Formula electronic equipment is big in order to meet although researchers are innumerable to research of the rechargeable battery in energy storage field The market demand, it is necessary to develop specific capacity higher (>600mAh·g-1), capacity is played stably, the negative material of excellent high rate performance.
Transiton metal binary oxides zinc metastannate (ZnSnO3) since it is with high theoretical specific capacity (1317mAhg-1) and the advantages of rich reserves be considered as most potential to be applied to high-energy-density or power-type lithium ion battery in future Electrode material.But ZnSnO3There is also its essential defect, can not still obtain at present can practical application with binary transition metal Oxide is the lithium ion battery of anode.Main cause has：(1)、ZnSnO3It can be sent out in the repeatedly embedded of Li and during deviating from Raw volumetric expansion, ultimately results in dusting and it is lost electrical contact with collector.(2)、ZnSnO3Electric conductivity it is poor, electronics or Ionic conductivity is low, and reaction invertibity reduces too fast.
The content of the invention
The invention aims to solve existing ZnSnO3The problem of specific capacity is low and high rate performance is poor, and provide a kind of The preparation method and application of the hollow micron cube composite material of carbon coating zinc metastannate.
A kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate, it is specifically complete according to the following steps Into：
First, solution is prepared：
1., zinc chloride and citric acid be dissolved into deionized water, obtain the mixed liquor of zinc chloride and citric acid；
Step 1 1. described in the quality of zinc chloride and the volume ratio of deionized water be (0.1g~0.5g):20mL；
Step 1 1. described in the quality of citric acid and the volume ratio of deionized water be (0.2g~0.5g):20mL；
2., butter of tin is dissolved into absolute ethyl alcohol, obtain butter of tin solution；
Step 1 2. described in the quality of butter of tin and the volume ratio of absolute ethyl alcohol be (0.5g~0.9g):10mL；
3., NaOH is dissolved into deionized water, obtain NaOH solution；
Step 1 3. described in the quality of NaOH and the volume ratio of deionized water be (1g~4g):40mL；
2nd, low whipping speed be 1000r/min~1500r/min under conditions of by the mixed liquor of zinc chloride and citric acid with Butter of tin solution mixes, and adds NaOH and deionized water, then low whipping speed is to be stirred under 1500r/min~2000r/min Reaction 20min~40min is mixed, adds NaOH solution, then low whipping speed is to be stirred instead under 1500r/min~2000r/min 0.5h~2h is answered, obtains reaction solution；
The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of butter of tin solution are (15~25): (5~15)；
The quality of NaOH described in step 2 and the volume ratio of butter of tin solution are (0.7g~1g):10mL；
Deionized water and the volume ratio of butter of tin solution described in step 2 are (40~60):10mL；
The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of NaOH solution are (15~25):40；
3rd, reaction solution is centrifuged in the case where centrifugal speed is 3500r/min~4000r/min, removes supernatant, reacted Product；Reaction product is cleaned 3 times~4 times using deionized water, then is done in the vacuum drying chamber that temperature is 70 DEG C~90 DEG C Dry 10h~14h, obtains hollow ZnSn (OH)6White powder；
4th, by hollow ZnSn (OH)6White powder is put into tube furnace, then nitrogen is passed through into tube furnace, by tube furnace With the heating rate of 1 DEG C/min from room temperature to 450 DEG C~550 DEG C, then in nitrogen atmosphere and temperature it is 450 DEG C~550 DEG C Lower calcining 1h~3h, obtains hollow ZnSnO3Micron cube；
5th, by hollow ZnSnO3Micron cube and glucose are added in deionized water, are placed into hydrothermal reaction kettle, then Hydrothermal reaction kettle is warming up to 170 DEG C~190 DEG C, then hydro-thermal reaction 10h~14h at 170 DEG C~190 DEG C, it is anti-to obtain hydro-thermal Answer product；
ZnSnO described in step 53The volume ratio of the cubical quality of micron and deionized water is (0.2g~0.3g): 30mL；
The quality of glucose described in step 5 and the volume ratio of deionized water are (0.3g~0.6g):30mL；
6th, hydro-thermal reaction product is dried into 10h~14h in the case where temperature is 70 DEG C~90 DEG C, placed into tube furnace, then to Argon gas is passed through in tube furnace, then tube furnace is warming up to 400 DEG C~500 DEG C with the programming rate of 1 DEG C/min, then in argon gas atmosphere It is that 3h~5h is calcined at 400 DEG C~500 DEG C with temperature, obtains the hollow micron cube composite material of carbon coating zinc metastannate.
Advantages of the present invention：
First, the present invention constructs the ZnSnO of hollow-core construction3, to the ZnSnO of hollow-core construction3Carbon coating is carried out, structure is hollow Structure not only can promote the transport of ion by shortening diffusion length, and can be by increasing active material and electrolysis The contact area of liquid improves electrolyte wetability；And carbon coating can not only improve its electric conductivity, and them can be suppressed Volumetric expansion and the shortcomings of overcome it easily to reunite, so as to improve ZnSnO3Storage lithium characteristic；
2nd, the present invention prepares hollow ZnSnO using coprecipitation-calcination method3Cube, then it is empty with the centering of glucose hydro-thermal ZnSnO3Cube carries out carbon coating, obtains the hollow micron cube composite material of carbon coating zinc metastannate, what the present invention used Raw material sources enrich, and whole experiment process is easy to operate, of low cost, and product possesses high rate charge-discharge characteristic and circulation Stability, can be used as lithium ion battery negative material；
3rd, the hollow micron cube composite material of carbon coating zinc metastannate prepared using the present invention is born as lithium ion battery First five the circle specific discharge capacity of lithium ion battery prepared by pole material in the case where current density is 100mA/g respectively may be about 1607mAh/ G, 1045mAh/g, 966mAh/g, 937mAh/g, 912mAh/g, after the 3rd circle, the hollow micron of carbon coating zinc metastannate is stood The special capacity fade of cube composite material substantially diminishes, and the opposite 3rd circle capacity retention ratio of the 5th circle is up to 94%, and by 100 The hollow micron cube composite material of carbon coating zinc metastannate prepared after secondary circulation using the present invention is used as negative electrode of lithium ion battery Lithium ion battery prepared by material still keeps more than 820mAh/g.
The present invention can obtain a kind of hollow micron cube composite material of carbon coating zinc metastannate.
Brief description of the drawings
Fig. 1 is ZnSn (OH)6XRD spectrum, the 1 hollow ZnSn (OH) prepared for one step 3 of embodiment in Fig. 16White The XRD curves of powder, 2 be ZnSn (OH)6Standard x RD curves；
Fig. 2 is hollow ZnSnO3The XRD of micron cube and the hollow micron cube composite material of carbon coating zinc metastannate Collection of illustrative plates, the 1 hollow ZnSnO prepared for one step 4 of embodiment in Fig. 23The cubical XRD curves of micron, 2 be one step of embodiment The XRD curves of the rapid six hollow micron cube composite materials of carbon coating zinc metastannate prepared；
Fig. 3 is hollow ZnSnO prepared by one step 4 of embodiment3The cubical SEM figures of micron；
Fig. 4 is the SEM figures of the hollow micron cube composite material of carbon coating zinc metastannate prepared by one step 6 of embodiment；
Fig. 5 is hollow ZnSnO prepared by one step 4 of embodiment3The cubical TEM figures of micron；
Fig. 6 is the TEM figures of the hollow micron cube composite material of carbon coating zinc metastannate prepared by one step 6 of embodiment；
Fig. 7 is the hollow ZnSnO prepared with one step 4 of embodiment3Micron cube is as lithium ion battery negative material The charging and discharging curve of first five circle of the lithium ion battery of preparation, in Fig. 71 be first lap charging and discharging curve, 2 for the second circle charge and discharge Electric curve, 3 be the 3rd charging and discharging curve enclosed, and 4 be the 4th charging and discharging curve enclosed, and 5 be the charging and discharging curve of the 5th circle；
Fig. 8 is that the hollow micron cube composite material of carbon coating zinc metastannate prepared using one step 6 of embodiment is used as lithium The charging and discharging curve of first five circle of lithium ion battery prepared by ion battery cathode material, 1 is bent for the discharge and recharge of first lap in Fig. 8 Line, 2 be the second charging and discharging curve enclosed, and 3 be the 3rd charging and discharging curve enclosed, and 4 be the charging and discharging curve of the 4th circle, and 5 be the 5th The charging and discharging curve of circle；
Fig. 9 is cycle performance figure, and 1 is the hollow ZnSnO prepared with one step 4 of embodiment in Fig. 93Micron cube is made The cycle performance curve of the lithium ion battery prepared for lithium ion battery negative material, 2 be to be prepared with one step 6 of embodiment The lithium ion battery that the hollow micron cube composite material of carbon coating zinc metastannate is prepared as lithium ion battery negative material Cycle performance curve；
Figure 10 is high rate performance curve under different current densities, and 1 is to be prepared with one step 4 of embodiment in Figure 10 Hollow ZnSnO3Micron cube is as lithium ion battery prepared by lithium ion battery negative material under different current densities High rate performance curve, 2 be that the hollow micron cube composite material of carbon coating zinc metastannate prepared with one step 6 of embodiment is made High rate performance curve of the lithium ion battery under different current densities prepared for lithium ion battery negative material；
Figure 11 be using one step 6 of embodiment prepare the hollow micron cube composite material of carbon coating zinc metastannate as The charging and discharging curves of preceding four circle of sodium-ion battery prepared by anode material of lithium-ion battery, in Figure 11 1 be first lap charge and discharge Electric curve, 2 be the second charging and discharging curve enclosed, and 3 be the 3rd charging and discharging curve enclosed, and 4 be the charging and discharging curve of the 4th circle；
Figure 12 be using one step 6 of embodiment prepare the hollow micron cube composite material of carbon coating zinc metastannate as The cycle performance curve of sodium-ion battery prepared by anode material of lithium-ion battery, 1 is charging in Figure 12, and 2 be electric discharge.
Embodiment
Embodiment one：Present embodiment is a kind of hollow micron cube composite material of carbon coating zinc metastannate Preparation method, is specifically realized by the following steps：
First, solution is prepared：
1., zinc chloride and citric acid be dissolved into deionized water, obtain the mixed liquor of zinc chloride and citric acid；
Step 1 1. described in the quality of zinc chloride and the volume ratio of deionized water be (0.1g~0.5g):20mL；
Step 1 1. described in the quality of citric acid and the volume ratio of deionized water be (0.2g~0.5g):20mL；
2., butter of tin is dissolved into absolute ethyl alcohol, obtain butter of tin solution；
Step 1 2. described in the quality of butter of tin and the volume ratio of absolute ethyl alcohol be (0.5g~0.9g):10mL；
3., NaOH is dissolved into deionized water, obtain NaOH solution；
Step 1 3. described in the quality of NaOH and the volume ratio of deionized water be (1g~4g):40mL；
2nd, low whipping speed be 1000r/min~1500r/min under conditions of by the mixed liquor of zinc chloride and citric acid with Butter of tin solution mixes, and adds NaOH and deionized water, then low whipping speed is to be stirred under 1500r/min~2000r/min Reaction 20min~40min is mixed, adds NaOH solution, then low whipping speed is to be stirred instead under 1500r/min~2000r/min 0.5h~2h is answered, obtains reaction solution；
The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of butter of tin solution are (15~25): (5~15)；
The quality of NaOH described in step 2 and the volume ratio of butter of tin solution are (0.7g~1g):10mL；
Deionized water and the volume ratio of butter of tin solution described in step 2 are (40~60):10mL；
The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of NaOH solution are (15~25):40；
3rd, reaction solution is centrifuged in the case where centrifugal speed is 3500r/min~4000r/min, removes supernatant, reacted Product；Reaction product is cleaned 3 times~4 times using deionized water, then is done in the vacuum drying chamber that temperature is 70 DEG C~90 DEG C Dry 10h~14h, obtains hollow ZnSn (OH)6White powder；
4th, by hollow ZnSn (OH)6White powder is put into tube furnace, then nitrogen is passed through into tube furnace, by tube furnace With the heating rate of 1 DEG C/min from room temperature to 450 DEG C~550 DEG C, then in nitrogen atmosphere and temperature it is 450 DEG C~550 DEG C Lower calcining 1h~3h, obtains hollow ZnSnO3Micron cube；
5th, by hollow ZnSnO3Micron cube and glucose are added in deionized water, are placed into hydrothermal reaction kettle, then Hydrothermal reaction kettle is warming up to 170 DEG C~190 DEG C, then hydro-thermal reaction 10h~14h at 170 DEG C~190 DEG C, it is anti-to obtain hydro-thermal Answer product；
ZnSnO described in step 53The volume ratio of the cubical quality of micron and deionized water is (0.2g~0.3g): 30mL；
The quality of glucose described in step 5 and the volume ratio of deionized water are (0.3g~0.6g):30mL；
6th, hydro-thermal reaction product is dried into 10h~14h in the case where temperature is 70 DEG C~90 DEG C, placed into tube furnace, then to Argon gas is passed through in tube furnace, then tube furnace is warming up to 400 DEG C~500 DEG C with the programming rate of 1 DEG C/min, then in argon gas atmosphere It is that 3h~5h is calcined at 400 DEG C~500 DEG C with temperature, obtains the hollow micron cube composite material of carbon coating zinc metastannate.
The advantages of present embodiment：
First, present embodiment constructs the ZnSnO of hollow-core construction3, to the ZnSnO of hollow-core construction3Carry out carbon coating, structure Hollow-core construction not only can promote the transport of ion by shortening diffusion length, and can by increase active material with The contact area of electrolyte improves electrolyte wetability；And carbon coating can not only improve its electric conductivity, and can suppress Their volumetric expansion and the shortcomings of overcome it easily to reunite, so as to improve ZnSnO3Storage lithium characteristic；
2nd, present embodiment prepares hollow ZnSnO using coprecipitation-calcination method3Cube, then with glucose hydro-thermal centering Empty ZnSnO3Cube carries out carbon coating, obtains the hollow micron cube composite material of carbon coating zinc metastannate, present embodiment The raw material sources used enrich, and whole experiment process is easy to operate, of low cost, and product possesses high rate charge-discharge characteristic And cyclical stability, lithium ion battery negative material can be used as；
3rd, the hollow micron cube composite material of carbon coating zinc metastannate prepared using present embodiment is used as lithium-ion electric First five the circle specific discharge capacity of lithium ion battery prepared by pond negative material in the case where current density is 100mA/g respectively may be about 1607mAh/g, 1045mAh/g, 966mAh/g, 937mAh/g, 912mAh/g, after the 3rd circle, in carbon coating zinc metastannate The special capacity fade of empty micron cube composite material substantially diminishes, and the opposite 3rd circle capacity retention ratio of the 5th circle is up to 94%, And the hollow micron cube composite material of carbon coating zinc metastannate prepared after 100 circulations using present embodiment is used as lithium Lithium ion battery prepared by ion battery cathode material still keeps more than 820mAh/g.
Present embodiment can obtain a kind of hollow micron cube composite material of carbon coating zinc metastannate.
Embodiment two：Present embodiment is with one difference of embodiment：Step 1 1. described in chlorine It is (0.2g~0.3g) to change the quality of zinc and the volume ratio of deionized water:20mL.Other steps are identical with embodiment one.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Step 1 1. in The quality of the citric acid and the volume ratio of deionized water are (0.3g~0.4g):20mL.Other steps and specific embodiment party Formula one or two is identical.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Step 1 2. in The quality of the butter of tin and the volume ratio of absolute ethyl alcohol are (0.5g~0.7g):10mL.Other steps and specific implementation Mode one to three is identical.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Step 1 3. in The quality of the NaOH and the volume ratio of deionized water are (2g~3g):40mL.Other steps and embodiment one to Four is identical.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Will in step 4 Hollow ZnSn (OH)6White powder is put into tube furnace, then nitrogen is passed through into tube furnace, by tube furnace with the liter of 1 DEG C/min Warm speed calcined from room temperature to 480 DEG C~500 DEG C, then at being 480 DEG C~500 DEG C in nitrogen atmosphere and temperature 1.5h~ 2h, obtains hollow ZnSnO3Micron cube.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Will in step 5 Hollow ZnSnO3Micron cube and glucose are added in deionized water, are placed into hydrothermal reaction kettle, then by hydrothermal reaction kettle 175 DEG C~180 DEG C, then hydro-thermal reaction 10h~12h at 175 DEG C~180 DEG C are warming up to, obtains hydro-thermal reaction product.Other steps Suddenly it is identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Will in step 6 Dry 10h~12h at hydro-thermal reaction product is 75 DEG C~80 DEG C in temperature, places into tube furnace, then be passed through into tube furnace Argon gas, then tube furnace is warming up to 430 DEG C~450 DEG C with the programming rate of 1 DEG C/min, then in argon gas atmosphere and temperature be 430 DEG C~450 DEG C at calcine 3h~4h, obtain the hollow micron cube composite material of carbon coating zinc metastannate.Other steps with it is specific Embodiment one to seven is identical.
Embodiment nine：Present embodiment is that a kind of hollow micron cube composite material of carbon coating zinc metastannate is made To prepare lithium ion battery negative material application.
Embodiment ten：Present embodiment is that a kind of hollow micron cube composite material of carbon coating zinc metastannate is made To prepare anode material of lithium-ion battery application.
Beneficial effects of the present invention are verified using following embodiments：
Embodiment one：A kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate, is specifically pressed What following steps were completed：
First, solution is prepared：
1., 0.27g zinc chloride and 0.38g citric acids be dissolved into 20mL deionized waters, obtain zinc chloride and citric acid Mixed liquor；
2., 0.7g butters of tin are dissolved into 10mL absolute ethyl alcohols, obtain butter of tin solution；
3., 3g NaOH are dissolved into 40mL deionized waters, obtain NaOH solution；
2nd, under conditions of low whipping speed is 1300r/min by step 1 1. in obtained zinc chloride and citric acid it is mixed The butter of tin solution mixing obtained in closing liquid and step 1 2., adds 0.82g NaOH and 50mL deionized waters, then stirring Speed is mixed as stirring reaction 30min, the NaOH solution obtained in adding step 1 3., then low whipping speed under 1700r/min For stirring reaction 1h under 1700r/min, reaction solution is obtained；
3rd, reaction solution is centrifuged in the case where centrifugal speed is 3600r/min, removes supernatant, obtain reaction product；Using going Ionized water cleans reaction product 4 times, then the dry 12h in the vacuum drying chamber that temperature is 80 DEG C, obtains hollow ZnSn (OH)6 White powder；
4th, by hollow ZnSn (OH)6White powder is put into tube furnace, then nitrogen is passed through into tube furnace, by tube furnace With the heating rate of 1 DEG C/min from room temperature to 500 DEG C, then 2h is calcined at being 500 DEG C in nitrogen atmosphere and temperature, in obtaining Empty ZnSnO3Micron cube；
5th, by the hollow ZnSnO of 0.23g3Micron cube and 0.45g glucose are added in 30mL deionized waters, are placed into In hydrothermal reaction kettle, then hydrothermal reaction kettle is warming up to 180 DEG C, then the hydro-thermal reaction 12h at 180 DEG C, obtains hydro-thermal reaction production Thing；
6th, hydro-thermal reaction product is dried into 12h in the case where temperature is 80 DEG C, placed into tube furnace, then lead into tube furnace Enter argon gas, then tube furnace is warming up to 450 DEG C with the programming rate of 1 DEG C/min, then forged at being 450 DEG C in argon gas atmosphere and temperature 4h is burnt, obtains the hollow micron cube composite material of carbon coating zinc metastannate.
Fig. 1 is ZnSn (OH)6XRD spectrum, the 1 hollow ZnSn (OH) prepared for one step 3 of embodiment in Fig. 16White The XRD curves of powder, 2 be ZnSn (OH)6Standard x RD curves；
Curve 2 is ZnSn (OH) in Fig. 16Standard spectrogram (JCPDS 74-1825).
From fig. 1, it can be seen that hollow ZnSn (OH) prepared by one step 3 of embodiment6The diffraction maximum peak shape of white powder is sharp, And peak position 2 θ=19.6 °, 22.7 °, 32.4 °, 36.3 °, 38.2 °, 40.0 °, 46.5 °, 52.4 °, 57.8 °, 67.9 °, 72.6 ° With 77.3 ° at ZnSn (OH)6Unanimously, the diffraction maximum of no other impurity exists standard spectrogram (JCPDS 74-1825), illustrates real Apply the hollow ZnSn (OH) of one step 3 of example preparation6White powder has higher crystallinity.
Fig. 2 is hollow ZnSnO3The XRD of micron cube and the hollow micron cube composite material of carbon coating zinc metastannate Collection of illustrative plates, the 1 hollow ZnSnO prepared for one step 4 of embodiment in Fig. 23The cubical XRD curves of micron, 2 be one step of embodiment The XRD curves of the rapid six hollow micron cube composite materials of carbon coating zinc metastannate prepared；
As can be seen from Figure 2, nearby there are 2 weak peaks for about 33 ° and 59 ° in 2 θ in curve 1 in Fig. 2, is in addition not observed Other obvious diffraction maximums, this explanation generate unformed ZnSnO3.Curve 2 can learn the inclined tin after bag carbon from Fig. 2 There is a weak broad peak (carbon peak) at 25.6 ° in sour zinc.
Fig. 3 is hollow ZnSnO prepared by one step 4 of embodiment3The cubical SEM figures of micron；
As can be seen from Figure 3；Hollow ZnSnO prepared by one step 4 of embodiment3Micron cube is in cube structure, and size exists 1 μm or so.
Fig. 4 is the SEM figures of the hollow micron cube composite material of carbon coating zinc metastannate prepared by one step 6 of embodiment；
As can be seen from Figure 4；ZnSnO after carbon coating3Cube structure is still kept, size does not change significantly, but can be with See that cube face has supported many carbon dotss.
Fig. 5 is hollow ZnSnO prepared by one step 4 of embodiment3The cubical TEM figures of micron；
It can be seen that hollow ZnSnO from transmission plot Fig. 53Micron cube is internally hollow, wall thickness about 100nm.
Fig. 6 is the TEM figures of the hollow micron cube composite material of carbon coating zinc metastannate prepared by one step 6 of embodiment；
As can be seen from Figure 6, carbon-coated ZnSnO3Micron cube still keeps its hollow-core construction, it may be clearly seen that cladding Carbon layers having thicknesses be about 30nm~50nm.
Embodiment two：Using embodiment one prepare the hollow micron cube composite material of carbon coating zinc metastannate as lithium from The process that sub- cell negative electrode material prepares lithium ion battery is as follows：
(1), carbon coating zinc metastannate hollow micron cube composite material, acetylene black and the quality prepared embodiment one The ptfe emulsion that fraction is 5% is according to quality micron cube more hollow than carbon coating zinc metastannate prepared by embodiment one Composite material:Acetylene black:The ptfe emulsion that mass fraction is 5% is 50:30:20 are uniformly mixed, and form slurry；
Ptfe emulsion described in step (1) evenly spreads to 1-methyl-2-pyrrolidinone for polytetrafluorethylepowder powder In obtained mixture；
(2), slurry is uniformly coated in the nickel foam weighed of a diameter of 12mm, obtains pole piece；Again in temperature Spend and be dried in vacuo 10h for 80 DEG C, obtain disk, be re-weighed, the carbon bag that in the pole piece prepared by embodiment one is obtained using difference assay Cover the quality of the hollow micron cube composite material of zinc metastannate；
(3), using tablet press machine, tabletting is carried out to disk in the case where pressure is 20MPa, obtains cathode pole piece；(4), in argon gas In atmosphere glove box, using CR2025 button cells shell as battery case, by cathode pole piece-membrane-positive plate (lithium piece) certainly Order on down stacks, and electrolyte is the LiPF of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and 1mol/L6It is molten Liquid is according to volume ratio 1:1:1:1 mixes；Gasket is the stainless steel substrates of 16.2mm × 1mm (diameter × thickness)；Detained again Lid and sealing, complete the assembling of button cell, obtain button cell；Button cell is stood into 12h at normal temperatures, obtains battery Activation.
Embodiment three：The hollow ZnSnO prepared with one step 4 of embodiment3Micron cube is as negative electrode of lithium ion battery The process that material prepares lithium ion battery is as follows：
(1), the hollow ZnSnO for preparing one step 4 of embodiment3Micron cube, acetylene black and mass fraction are 5% Ptfe emulsion according to quality than hollow ZnSnO prepared by one step 4 of embodiment3Micron cube:Acetylene black:Matter It is 50 to measure the ptfe emulsion that fraction is 5%:30:20 are uniformly mixed, and form slurry；
Ptfe emulsion described in step (1) evenly spreads to 1-methyl-2-pyrrolidinone for polytetrafluorethylepowder powder In obtained mixture；
(2), slurry is uniformly coated in the nickel foam weighed of a diameter of 12mm, obtains pole piece；Again in temperature Spend and be dried in vacuo 10h for 80 DEG C, obtain disk, be re-weighed, obtaining one step 4 of embodiment in the pole piece using difference assay prepares Hollow ZnSnO3The cubical quality of micron；
(3), using tablet press machine, tabletting is carried out to disk in the case where pressure is 20MPa, obtains cathode pole piece；(4), in argon gas In atmosphere glove box, using CR2025 button cells shell as battery case, by cathode pole piece-membrane-positive plate (lithium piece) certainly Order on down stacks, and electrolyte is the LiPF of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and 1mol/L6It is molten Liquid is according to volume ratio 1:1:1:1 mixes；Gasket is the stainless steel substrates of 16.2mm × 1mm (diameter × thickness)；Detained again Lid and sealing, complete the assembling of button cell, obtain button cell；Button cell is stood into 12h at normal temperatures, obtains battery Activation.
It is 100mA/g in current density, under conditions of charging/discharging voltage scope is 0-3V, to embodiment two and embodiment three The electrical property of button cell after the activation of preparation is tested, as shown in figs. 7-9.
Fig. 7 is the hollow ZnSnO prepared with one step 4 of embodiment3Micron cube is as lithium ion battery negative material The charging and discharging curve of first five circle of the lithium ion battery of preparation, in Fig. 71 be first lap charging and discharging curve, 2 for the second circle charge and discharge Electric curve, 3 be the 3rd charging and discharging curve enclosed, and 4 be the 4th charging and discharging curve enclosed, and 5 be the charging and discharging curve of the 5th circle；
It can be seen from figure 7 that hollow ZnSnO prepared by one step 4 of embodiment3Micron cube is as lithium-ion electric The first lap specific discharge capacity of lithium ion battery prepared by pond negative material is 1530mAh/g；Second, which encloses charging and discharging capacity, is 994mAh/g；3rd circle charging and discharging capacity is 922mAh/g；4th circle charging and discharging capacity is 865mAh/g；5th circle charge and discharge Electric specific capacity is 837mAh/g.
Fig. 8 is that the hollow micron cube composite material of carbon coating zinc metastannate prepared using one step 6 of embodiment is used as lithium The charging and discharging curve of first five circle of lithium ion battery prepared by ion battery cathode material, 1 is bent for the discharge and recharge of first lap in Fig. 8 Line, 2 be the second charging and discharging curve enclosed, and 3 be the 3rd charging and discharging curve enclosed, and 4 be the charging and discharging curve of the 4th circle, and 5 be the 5th The charging and discharging curve of circle；
As can be seen from Figure 8, the hollow micron cube bluk recombination of carbon coating zinc metastannate that prepared by one step 6 of embodiment The first lap specific discharge capacity for the lithium ion battery that material is prepared as lithium ion battery negative material is 1607mAh/g；Second Circle specific discharge capacity is 1034mAh/g；3rd circle specific discharge capacity is 956mAh/g；4th circle specific discharge capacity is 937mAh/ g；5th circle specific discharge capacity is 916mAh/g.After the 3rd circle, the hollow micron cube composite wood of carbon coating zinc metastannate The special capacity fade of material substantially diminishes, and the opposite 3rd circle capacity retention ratio of the 5th circle is up to 94%, and performance is better than ZnSnO3Electrode.
Fig. 9 is cycle performance figure, and 1 is the hollow ZnSnO prepared with one step 4 of embodiment in Fig. 93Micron cube is made The cycle performance curve of the lithium ion battery prepared for lithium ion battery negative material, 2 be to be prepared with one step 6 of embodiment The lithium ion battery that the hollow micron cube composite material of carbon coating zinc metastannate is prepared as lithium ion battery negative material Cycle performance curve；
9 as can be seen that under conditions of current density is 100mA/g after 100 discharge and recharge reactions from figure, circulates Service life stablizes in 820mAh/g, this is significantly larger than ZnSnO under the conditions of same current density3The specific capacity 211mAh/g of electrode.
Be 0~3V in charging/discharging voltage, current density 100mAh/g, 200mAh/g, 400mAh/g, 800mAh/g, Tested under conditions of 1600mAh/g, as shown in Figure 10；
Figure 10 is high rate performance curve under different current densities, and 1 is to be prepared with one step 4 of embodiment in Figure 10 Hollow ZnSnO3Micron cube is as lithium ion battery prepared by lithium ion battery negative material under different current densities High rate performance curve, 2 be that the hollow micron cube composite material of carbon coating zinc metastannate prepared with one step 6 of embodiment is made High rate performance curve of the lithium ion battery under different current densities prepared for lithium ion battery negative material；
From Figure 10 curve 2 as can be seen that current density be respectively 100mAh/g, 200mAh/g, 400mAh/g, Under conditions of 800mAh/g and 1600mA/g, with the hollow micron cube of carbon coating zinc metastannate of one step 6 of embodiment preparation The reversible specific capacity for the lithium ion battery that composite material is prepared as lithium ion battery negative material reaches 912mAh/g respectively, 736mAh/g, 616mAh/g, 502mAh/g and 386mAh/g be significantly larger than under same current density with one step 4 of embodiment The hollow ZnSnO prepared3The lithium ion battery (curve 1 in Figure 10) that micron cube is prepared as lithium ion battery negative material Reversible specific capacity (8120mAh/g, 5890mAh/g, 4670mAh/g, 3700mAh/g and 273mAh/g).
Example IV：The hollow micron cube composite material of carbon coating zinc metastannate prepared with one step 6 of embodiment is made The process of the sodium-ion battery prepared for anode material of lithium-ion battery is as follows：
(1), carbon coating zinc metastannate hollow micron cube composite material, acetylene black and the quality prepared embodiment one The ptfe emulsion that fraction is 5% is according to quality micron cube more hollow than carbon coating zinc metastannate prepared by embodiment one Composite material:Acetylene black:The ptfe emulsion that mass fraction is 5% is 50:30:20 are uniformly mixed, and form slurry；
Ptfe emulsion described in step (1) evenly spreads to 1-methyl-2-pyrrolidinone for polytetrafluorethylepowder powder In obtained mixture；
(2), slurry is uniformly coated in the nickel foam weighed of a diameter of 12mm, obtains pole piece；Again in temperature Spend and be dried in vacuo 10h for 80 DEG C, obtain disk, be re-weighed, the carbon bag that in the pole piece prepared by embodiment one is obtained using difference assay Cover the quality of the hollow micron cube composite material of zinc metastannate；
(3), using tablet press machine, tabletting is carried out to disk in the case where pressure is 20MPa, obtains cathode pole piece；(4), in argon gas In atmosphere glove box, using CR2025 button cells shell as battery case, by cathode pole piece-membrane-positive plate (sodium piece) certainly Order on down stacks, electrolyte NaClO4, propene carbonate, diethyl carbonate and fluorinated ethylene carbonate mixing Liquid；Gasket is the stainless steel substrates of 16.2mm × 1mm (diameter × thickness)；Buckle closure and sealing are carried out again, complete the dress of button cell Match somebody with somebody, obtain button cell；Button cell is stood into 12h at normal temperatures, is activated battery；
NaClO in electrolyte described in step (4)4Concentration be 1mol/L, the mass fraction of fluorinated ethylene carbonate For 5%, the volume ratio of propene carbonate and diethyl carbonate is 1:1.
It is 50mA/g in current density, under conditions of charging/discharging voltage scope is 0~3V, to one step 6 system of embodiment The sodium ion electricity that the hollow micron cube composite material of standby carbon coating zinc metastannate is prepared as anode material of lithium-ion battery The electrical property in pond is tested, as shown in Figure 11~12.
Figure 11 be using one step 6 of embodiment prepare the hollow micron cube composite material of carbon coating zinc metastannate as The charging and discharging curves of preceding four circle of sodium-ion battery prepared by anode material of lithium-ion battery, in Figure 11 1 be first lap charge and discharge Electric curve, 2 be the second charging and discharging curve enclosed, and 3 be the 3rd charging and discharging curve enclosed, and 4 be the charging and discharging curve of the 4th circle；
It can be seen from fig. 11 that answered with the hollow micron cube of carbon coating zinc metastannate prepared by one step 6 of embodiment The first lap specific discharge capacity for the sodium-ion battery that condensation material is prepared as anode material of lithium-ion battery is 710mAh/g；Second Circle specific discharge capacity is 296mAh/g；3rd circle specific discharge capacity is 276mAh/g；4th circle specific discharge capacity is 260mAh/g； The capacity retention ratio of opposite second circle of 4th circle is up to 88%.
Figure 12 be using one step 6 of embodiment prepare the hollow micron cube composite material of carbon coating zinc metastannate as The cycle performance curve of sodium-ion battery prepared by anode material of lithium-ion battery, 1 is charging in Figure 12, and 2 be electric discharge；
As can be seen from Figure 12；The hollow micron cube composite material of carbon coating zinc metastannate prepared with one step 6 of embodiment Pass through 40 charge and discharges under conditions of current density is 50mA/g as sodium-ion battery prepared by anode material of lithium-ion battery After electricity reaction, cycle life stabilization is in 130mAh/g.

Claims (10)

  1. A kind of a kind of 1. preparation method of the hollow micron cube composite material of carbon coating zinc metastannate, it is characterised in that carbon coating What the preparation method of the hollow micron cube composite material of zinc metastannate was specifically realized by the following steps：
    First, solution is prepared：
    1., zinc chloride and citric acid be dissolved into deionized water, obtain the mixed liquor of zinc chloride and citric acid；
    Step 1 1. described in the quality of zinc chloride and the volume ratio of deionized water be (0.1g~0.5g):20mL；
    Step 1 1. described in the quality of citric acid and the volume ratio of deionized water be (0.2g~0.5g):20mL；
    2., butter of tin is dissolved into absolute ethyl alcohol, obtain butter of tin solution；
    Step 1 2. described in the quality of butter of tin and the volume ratio of absolute ethyl alcohol be (0.5g~0.9g):10mL；
    3., NaOH is dissolved into deionized water, obtain NaOH solution；
    Step 1 3. described in the quality of NaOH and the volume ratio of deionized water be (1g~4g):40mL；
    2nd, by zinc chloride and the mixed liquor and tetrachloro of citric acid under conditions of low whipping speed is 1000r/min~1500r/min Change solution of tin mixing, add NaOH and deionized water, then low whipping speed is to be stirred instead under 1500r/min~2000r/min 20min~40min is answered, adds NaOH solution, then low whipping speed is that reaction is stirred under 1500r/min~2000r/min 0.5h~2h, obtains reaction solution；
    The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of butter of tin solution are (15~25):(5~ 15)；
    The quality of NaOH described in step 2 and the volume ratio of butter of tin solution are (0.7g~1g):10mL；
    Deionized water and the volume ratio of butter of tin solution described in step 2 are (40~60):10mL；
    The mixed liquor of zinc chloride and citric acid described in step 2 and the volume ratio of NaOH solution are (15~25):40；
    3rd, reaction solution is centrifuged in the case where centrifugal speed is 3500r/min~4000r/min, removes supernatant, obtain reaction production Thing；Reaction product is cleaned 3 times~4 times using deionized water, then the drying in the vacuum drying chamber that temperature is 70 DEG C~90 DEG C 10h~14h, obtains hollow ZnSn (OH)6White powder；
    4th, by hollow ZnSn (OH)6White powder is put into tube furnace, then nitrogen is passed through into tube furnace, by tube furnace with 1 DEG C/ The heating rate of min is calcined from room temperature to 450 DEG C~550 DEG C, then at being 450 DEG C~550 DEG C in nitrogen atmosphere and temperature 1h~3h, obtains hollow ZnSnO3Micron cube；
    5th, by hollow ZnSnO3Micron cube and glucose are added in deionized water, are placed into hydrothermal reaction kettle, then by water Thermal response kettle is warming up to 170 DEG C~190 DEG C, then hydro-thermal reaction 10h~14h at 170 DEG C~190 DEG C, obtains hydro-thermal reaction production Thing；
    ZnSnO described in step 53The volume ratio of the cubical quality of micron and deionized water is (0.2g~0.3g):30mL；
    The quality of glucose described in step 5 and the volume ratio of deionized water are (0.3g~0.6g):30mL；
    6th, by hydro-thermal reaction product be 70 DEG C~90 DEG C in temperature at dry 10h~14h, place into tube furnace, then to tubular type Argon gas is passed through in stove, then tube furnace is warming up to 400 DEG C~500 DEG C with the programming rate of 1 DEG C/min, then in argon gas atmosphere and temperature Spend to calcine 3h~5h at 400 DEG C~500 DEG C, obtain the hollow micron cube composite material of carbon coating zinc metastannate.
  2. 2. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that step 1 1. described in the quality of zinc chloride and the volume ratio of deionized water be (0.2g~0.3g):20mL.
  3. 3. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that step 1 1. described in the quality of citric acid and the volume ratio of deionized water be (0.3g~0.4g):20mL.
  4. 4. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that step 1 2. described in the quality of butter of tin and the volume ratio of absolute ethyl alcohol be (0.5g~0.7g): 10mL。
  5. 5. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that step 1 3. described in the quality of NaOH and the volume ratio of deionized water be (2g~3g):40mL.
  6. 6. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that by hollow ZnSn (OH) in step 46White powder is put into tube furnace, then nitrogen is passed through into tube furnace, will Tube furnace with the heating rate of 1 DEG C/min from room temperature to 480 DEG C~500 DEG C, then nitrogen atmosphere and temperature for 480 DEG C~ 1.5h~2h is calcined at 500 DEG C, obtains hollow ZnSnO3Micron cube.
  7. 7. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that by hollow ZnSnO in step 53Micron cube and glucose are added in deionized water, place into hydro-thermal reaction In kettle, then hydrothermal reaction kettle is warming up to 175 DEG C~180 DEG C, then hydro-thermal reaction 10h~12h at 175 DEG C~180 DEG C, obtained Hydro-thermal reaction product.
  8. 8. a kind of preparation method of the hollow micron cube composite material of carbon coating zinc metastannate according to claim 1, It is characterized in that hydro-thermal reaction product is dried 10h~12h in the case where temperature is 75 DEG C~80 DEG C in step 6, tube furnace is placed into In, then argon gas is passed through into tube furnace, then tube furnace is warming up to 430 DEG C~450 DEG C with the programming rate of 1 DEG C/min, then Argon gas atmosphere and temperature are that 3h~4h is calcined at 430 DEG C~450 DEG C, obtain the hollow micron cube bluk recombination of carbon coating zinc metastannate Material.
  9. 9. a kind of application of the hollow micron cube composite material of carbon coating zinc metastannate as claimed in claim 1, its feature It is that a kind of hollow micron cube composite material of carbon coating zinc metastannate is used as and prepares lithium ion battery negative material application.
  10. 10. a kind of application of the hollow micron cube composite material of carbon coating zinc metastannate as claimed in claim 1, its feature It is that a kind of hollow micron cube composite material of carbon coating zinc metastannate is used as and prepares anode material of lithium-ion battery application.
CN201711315812.5A 2017-12-11 2017-12-11 A kind of preparation method and application of the hollow micron cube composite material of carbon coating zinc metastannate Pending CN108039472A (en)

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CN109678198A (en) * 2018-12-17 2019-04-26 天津理工大学 A kind of synthetic method of the nano-zinc stannate material for N-shaped transparent semiconductor film
CN110061213A (en) * 2019-04-17 2019-07-26 中南大学 Hollow spheres carbon coating zinc stannate composite negative pole material and preparation method thereof
CN110247033A (en) * 2019-05-29 2019-09-17 广东工业大学 A kind of SnS@NSC core-bivalve cube structure composite material and preparation method and application
CN110289398A (en) * 2019-04-23 2019-09-27 武汉理工大学 Mesoporous carbon coating zine stannate nano bar material derived from a kind of metal organic framework and its preparation method and application
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CN111244423A (en) * 2020-01-19 2020-06-05 杭州电子科技大学 NiO-coated ZnSnO3Preparation method of cubic composite material
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CN113328074A (en) * 2021-03-16 2021-08-31 湖北工程学院 ZnSnO3Preparation method and application of/NC composite material
CN113707855A (en) * 2021-08-18 2021-11-26 大连大学 Lithium ion battery cathode composite material and preparation method thereof

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CN109279647B (en) * 2018-09-29 2020-12-01 中南大学 Preparation method of cubic nano zinc tin sulfide as negative electrode material of sodium ion battery
CN109279647A (en) * 2018-09-29 2019-01-29 中南大学 A kind of preparation method of the cubic nano-zinc sulfide tin of anode material of lithium-ion battery
CN109678198A (en) * 2018-12-17 2019-04-26 天津理工大学 A kind of synthetic method of the nano-zinc stannate material for N-shaped transparent semiconductor film
CN110061213A (en) * 2019-04-17 2019-07-26 中南大学 Hollow spheres carbon coating zinc stannate composite negative pole material and preparation method thereof
CN110061213B (en) * 2019-04-17 2020-07-17 中南大学 Hollow spherical carbon-coated zinc stannate composite negative electrode material and preparation method thereof
CN110289398A (en) * 2019-04-23 2019-09-27 武汉理工大学 Mesoporous carbon coating zine stannate nano bar material derived from a kind of metal organic framework and its preparation method and application
CN110247033A (en) * 2019-05-29 2019-09-17 广东工业大学 A kind of SnS@NSC core-bivalve cube structure composite material and preparation method and application
WO2021051908A1 (en) * 2019-09-16 2021-03-25 中国科学院青岛生物能源与过程研究所 Negative electrode material for sodium ion battery, preparation method therefor and use thereof
CN110828818B (en) * 2019-09-29 2021-03-19 郑州大学 Preparation method and application of carbon-coated manganese selenide hollow cubic three-dimensional material
CN110828818A (en) * 2019-09-29 2020-02-21 郑州大学 Preparation method and application of carbon-coated manganese selenide hollow cubic three-dimensional material
CN111244423A (en) * 2020-01-19 2020-06-05 杭州电子科技大学 NiO-coated ZnSnO3Preparation method of cubic composite material
CN113328074A (en) * 2021-03-16 2021-08-31 湖北工程学院 ZnSnO3Preparation method and application of/NC composite material
CN113707855A (en) * 2021-08-18 2021-11-26 大连大学 Lithium ion battery cathode composite material and preparation method thereof
CN113707855B (en) * 2021-08-18 2023-11-07 大连大学 Lithium ion battery negative electrode composite material and preparation method thereof

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Application publication date: 20180515