CN110380038A - Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys - Google Patents

Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys Download PDF

Info

Publication number
CN110380038A
CN110380038A CN201910670928.3A CN201910670928A CN110380038A CN 110380038 A CN110380038 A CN 110380038A CN 201910670928 A CN201910670928 A CN 201910670928A CN 110380038 A CN110380038 A CN 110380038A
Authority
CN
China
Prior art keywords
antimony
carbon
shell
embedding
antimony oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910670928.3A
Other languages
Chinese (zh)
Other versions
CN110380038B (en
Inventor
王志远
董康泽
罗绍华
刘延国
王庆
张亚辉
郝爱民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University Qinhuangdao Branch
Original Assignee
Northeastern University Qinhuangdao Branch
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University Qinhuangdao Branch filed Critical Northeastern University Qinhuangdao Branch
Priority to CN201910670928.3A priority Critical patent/CN110380038B/en
Publication of CN110380038A publication Critical patent/CN110380038A/en
Application granted granted Critical
Publication of CN110380038B publication Critical patent/CN110380038B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

A kind of pyrolysis carbon composite and preparation method embedding more shell antimony oxide-antimony alloys, belongs to cell negative electrode material technical field；The composite material is combined by carbon-coated nanoscale antimony-antimony alloy particle and pyrolytic carbon, and carbon-coated nanoscale antimony-antimony alloy particle is uniformly embedded in pyrolytic carbon；Preparation method: 1) by NaCl: carbon source: tin source mixing after magnetic agitation and complete jelly reality, carries out vacuum freezedrying with deionized water dissolving；2) it is once heat-treated, is cooled to room temperature；3) it washs, filter and dries；4) after drying, secondary heat treatment is carried out, room temperature is cooled to, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys is made.Composite material of the invention is as battery cathode in the test of potassium ion half-cell, and under certain current density, initial charge reversible capacity is 300~650mAh g‑1, after 25~100 circulations, capacity is 150~490mAh g‑1。

Description

Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys
Technical field
The invention belongs to cell negative electrode material technical fields, are related to a kind of kalium ion battery negative electrode material technology, specially A kind of pyrolysis carbon composite and preparation method embedding more shell antimony oxide-antimony alloys.
Background technique
Due to continuous exhausted and Global Environmental Problems the aggravation of traditional fossil energy, develops sustainable and clean energy resource and get over To be more taken seriously.Secondary cell is due to its high-energy conversion efficiency and portability, it has also become most promising energy storage device it One.Chemical property, natural resources abundant and the low cost having due to lithium ion, people are to kalium ion battery and have pole Big interest.
In recent years, carbon-based material is focused primarily upon for the research of kalium ion battery, but its theoretical specific capacity only has 280mAh/g is not able to satisfy the requirement of current development high-energy density kalium ion battery.Metallic antimony is up to 660mAh/ because of it The theoretical specific capacity of g has obtained extensive concern in recent years, but simple substance antimony is during potassium ion deintercalation, due to huge volume Expansion, structural stability are subject to destroy, and cause material cracks, dusting, to seriously affect cycle performance.Meanwhile simple substance That there is also first charge-discharge irreversible capacities is high for antimony material, and electric conductivity is deteriorated and influences high rate performance etc. when complete potassium-sodium alloy Problem.For the method for modifying of antimony cathode, mainly consider from the following aspects: one, it is metallic antimony and carbon is compound, it is steady using carbon Fixed basic framework alleviates volume expansion, it is made to have both the high theoretical capacity of the excellent cycle performance and antimony of carbon；Two, it makes Standby nanoscale antimony weakens volume of material during deintercalation potassium to a certain extent and becomes while shortening the diffusion path of potassium ion Change.Three, more shell structurres are prepared, its each layer during potassium is made to play synergistic effect.Above-mentioned three kinds of method of modifying are to raising Antimony oxide-antimony cathode performance has a certain effect, but cannot to be fully solved antimony oxide-antimony alloy composite material upper for single method State critical issue.
Summary of the invention
In view of the deficiencies of the prior art, it is compound to provide a kind of pyrolytic carbon for embedding more shell antimony oxide-antimony alloys by the present invention Material and preparation method.The material is combined by carbon-coated nanoscale antimony-antimony alloy particle and pyrolytic carbon, carbon packet Nanoscale antimony-antimony alloy the particle covered is uniformly embedded in pyrolytic carbon, and pyrolytic carbon is that carbon source is pyrolyzed at 400~800 DEG C The amorphous carbon of formation；More shells be then by outermost layer carbon, intermediate oxidation antimony and the inside antimony simple substance composition；The composite material As kalium ion battery cathode, there is the features such as capacity is high, good cycling stability, high rate performance is excellent.
The pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, the composite material are carbon-coated Nanoscale antimony-antimony alloy particle and pyrolytic carbon are combined, more shell structurres by control heat treatment time with Temperature is adjusted；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The cell negative electrode material is in the test of potassium ion half-cell, in 100~5000mA g-1Current density under, Initial charge reversible capacity is 300~650mAh g-1, after 25~100 circulations, capacity is 150~490mAh g-1.Table Excellent chemical property is revealed.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) template NaCl, antimony source and carbon source are mixed and is dissolved in deionized water, mixing is made in 3~12h of magnetic agitation Solution；Wherein, the molar ratio of carbon atom is 1:(10~500 in antimony ion contained in antimony source and carbon source), contained in antimony source The molar ratio of antimony ion and NaCl are 1:(100~500)；
(2) mixed solution made from after freezing reality completely, then carries out vacuum freezedrying, -70 in -40~-10 DEG C of pre-freezes Moisture removal is removed in vacuum drying under the conditions of~-10 DEG C, and then collecting dried object is presoma；
Step 2, primary heat treatment:
Presoma is put into crucible, is placed in tube furnace is heat-treated in an inert atmosphere, is warming up to 550~750 DEG C, is protected Cooled to room temperature after 2~5h of temperature, obtains intermediate product, wherein being passed through into tube furnace with the flow of 50~500mL/min Inert gas to exclude air, then with the flow of 50~200mL/min continues to be passed through inert gas；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Mixture after washing is dried under conditions of 60~80 DEG C, obtains powder；
Step 4, secondary heat treatment:
Powder is subjected to secondary heat treatment, at 200~340 DEG C, heat preservation 1~for 24 hours, it is cooled to room temperature under air atmosphere, i.e., It can obtain embedding the pyrolysis carbon composite of more shell antimony oxide-antimony alloys.
In the step 1, carbon source is one or more of citric acid, sucrose, glucose, starch, Victoria C；The antimony Source is one of antimony trichloride, antimony acetate, antimony tartrate or nitric acid antimony.
In the step 1, deionized water dosage >=NaCl solubility, i.e. the complete dissolved clarification of NaCl.
In the step 1, pre-freeze is carried out using refrigerator.
In the step 1, the pressure of freeze-drying is≤- 50pa.
In the step 2, heating condition are as follows: one or more of argon gas or helium are used as inert gas source.
In the step 2, the heating rate of heat treatment is 5~10 DEG C/min.
In the step 3, dried using baking oven.
In the step 4, heating condition are as follows: under air atmosphere, heating rate is 1~10 DEG C/min.
Vacuum drying removes moisture removal to keep the cubic structure of NaCl；Heat treatment process makes carbon source and carbon turn to carbon simple substance, gold Belong to ion and be reduced into metal simple-substance, metal simple-substance is assembled to form alloy.
The invention has the benefit that
(1) carbon coating antimony oxide prepared by the present invention-antimony more shells structure has buffered antimony negative electrode material in embedding de- potassium mistake Volume change in journey.Antimony oxide layer be introduced into so that antimony oxide-antimony electrode material antimony oxide can be in discharge process for the first time K is formed by conversion reaction2O and metallic antimony, K2O layers can be used as protective layer and further alleviate metallic antimony in charge and discharge process Volume expansion；The carbon-coating uniformly coated can not only inhibit alloying pellet to grow up during heat treatment, but also to metallic antimony Volume change also can play a buffer role in during deintercalation potassium.In addition, carbon material has the function of excellent electric conductivity and storage potassium, Its flexible volume change for also effectively buffering alloy in substrate.
(2) pyrolytic carbon for embedding more shell antimony oxide-antimony alloys that the present invention is prepared using dissolved salt template is compound Antimony oxide and antimony shell thickness is adjusted by the heat treatment of different temperatures and time in material, and preparation process is simple, safety, and Low production cost, the stable structure of formation, and there are excellent properties as kalium ion battery negative electrode material.
(3) simultaneously, secondary heat treatment process of the invention has extensive expansion, simple easily to implement, and is not limited to net The embedded antimony metal material of shape carbon structure is suitable for various forms and is pyrolyzed carbon coating antimony metal material.More shells of the method preparation Layer antimony oxide-antimony composite material has particle uniform, and good dispersion, large specific surface area, stable structure, specific capacity is high, cyclicity Can be good, and the advantage that high rate performance is excellent.
Detailed description of the invention
Fig. 1 present invention implements the SEM figure before 1~5 antimony oxide-antimony alloy composite material secondary heat treatment；
XRD spectrum before the antimony oxide of Fig. 2 embodiment of the present invention 1~5-antimony alloy composite material secondary heat treatment；
Negative electrode of lithium ion battery made from alloy composite materials before the secondary heat treatment of Fig. 3 embodiment of the present invention 1~5 Charge-discharge performance figure；
The antimony oxide of Fig. 4 embodiment of the present invention 1-240 DEG C of antimony alloy composite material secondary heat treatment, the SEM figure of 4h；
The antimony oxide of Fig. 5 embodiment of the present invention 1-240 DEG C of antimony alloy composite material secondary heat treatment, the XRD spectrum of 4h；
Kalium ion battery cathode fills made from alloy composite materials after the secondary heat treatment of Fig. 6 embodiment of the present invention 1 Discharge cycle performance figure；
The antimony oxide of Fig. 7 embodiment of the present invention 2-240 DEG C of antimony alloy composite material secondary heat treatment, the SEM figure of 12h；
The antimony oxide of Fig. 8 embodiment of the present invention 2-240 DEG C of antimony alloy composite material secondary heat treatment, the XRD spectrum of 12h；
Kalium ion battery cathode fills made from alloy composite materials after the secondary heat treatment of Fig. 9 embodiment of the present invention 2 Discharge cycle performance figure；
The antimony oxide of Figure 10 embodiment of the present invention 3-280 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum；
The antimony oxide of Figure 11 embodiment of the present invention 4-300 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum；
The antimony oxide of Figure 12 embodiment of the present invention 5-340 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum；
Specific embodiment
In the present embodiment 1~5 first time heat treatment after antimony oxide-antimony alloy composite material SEM, XRD and two The charge-discharge performance figure of negative electrode of lithium ion battery made from alloy composite materials before secondary heat treatment is identical.
Embodiment 1
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (20.64g), antimony source (SbCl3, 0.423g) and carbon source (citric acid, 2.5g) be dissolved in In ionized water (75ml), mixing clarification mixed solution is made in magnetic agitation 3h；
(2) pre-freeze in -10 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -40 DEG C, and then collecting dried object is presoma；
Step 2, primary heat treatment:
Presoma is put into crucible, argon gas is passed through with the flow of 200mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 200mL/min, 600 DEG C are warming up to, cooled to room temperature after 2h is kept the temperature, obtains To intermediate product A；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 60 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment:
Powder is subjected to secondary heat treatment, is warming up to 240 DEG C with the rate of heat addition of 1 DEG C/min, keeps the temperature 4h, under air atmosphere It is cooled to room temperature, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.
SEM figure before antimony oxide-antimony alloy composite material secondary heat treatment as shown in Figure 1, can be seen that carbon knot from the figure Structure and uniformly embedded nanoscale alloying pellet；Before antimony oxide-antimony alloy composite material secondary heat treatment as shown in Figure 2 XRD spectrum.Know that gained alloy is antimony oxide and antimony；In addition, antimony oxide has weak peak intensity, show that its thickness is smaller；Fig. 3 is The charge-discharge performance figure of negative electrode of lithium ion battery made from alloy composite materials before secondary heat treatment, it can be seen that 0.1A g-1Lower 100 reversible capacities of current density be 250mAh g-1。
Antimony oxide shown in Fig. 4-240 DEG C of antimony alloy composite material secondary heat treatment, the SEM figure of 4h, can be seen that from the figure Carbon structure and uniformly embedded nanoscale alloying pellet；Antimony oxide shown in Fig. 5-antimony alloy composite material secondary heat treatment 240 DEG C, the XRD spectrum of 4h.Know that gained alloy is antimony oxide-antimony alloy, in addition, the peak intensity increase of antimony oxide shows that its thickness increases Add；Fig. 6 is the charge-discharge performance figure of kalium ion battery cathode made from alloy composite materials after secondary heat treatment, can be with Find out in 0.1A g-1Lower 100 reversible capacities of current density be 480mAh g-1。
Embodiment 2
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (60.34g) antimony source (SbCl3, 0.423g) and carbon source (citric acid, 2.5g) be dissolved in In ionized water (75ml), clarification mixed solution is made in magnetic agitation 2h；
(2) pre-freeze in -15 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -45 DEG C, and then collecting dried object is presoma；
Step 2, primary heat treatment:
Presoma is put into crucible, argon gas is passed through with the flow of 200mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 200mL/min, 600 DEG C are warming up to, cooled to room temperature after 2h is kept the temperature, obtains To intermediate product；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 60 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment:
Obtained powder is subjected to secondary heat treatment, is warming up to 240 DEG C with the rate of heat addition of 1 DEG C/min, keeps the temperature 12h, it is empty It is cooled to room temperature under gas atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.
Antimony oxide -240 DEG C of antimony alloy composite material secondary heat treatment as shown in Figure 7, the SEM figure of 12h, can from the figure Carbon structure and uniformly embedded nanoscale alloying pellet out；Antimony oxide-antimony alloy composite material secondary heat treatment as shown in Figure 8 240 DEG C, the XRD spectrum of 12h.Know that gained alloy is that antimony oxide-antimony alloy, the furthermore peak intensity of antimony oxide and metallic antimony maintain an equal level； Fig. 9 is the charge-discharge performance figure of kalium ion battery cathode made from the alloy composite materials after secondary heat treatment, can be seen Out in 0.1A g-1Lower 100 reversible capacities of current density be 450mAh g-1。
Embodiment 3
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (20.85g), antimony source (SbCl3, 0.423g) and carbon source (citric acid, 2.5g) be dissolved in In ionized water (75ml), mixed solution is made in magnetic agitation 4h；
(2) pre-freeze in -10 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -45 DEG C, and then collecting dried object is presoma；
Step 2, it is heat-treated:
Presoma is put into crucible, argon gas is passed through with the flow of 100mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 50mL/min, 600 DEG C are warming up to, cooled to room temperature after 2h is kept the temperature, obtains Intermediate product；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 70 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment:
Obtained powder is subjected to secondary heat treatment, 280 DEG C is warming up to the rate of heat addition of 1 DEG C/min, keeps the temperature 4h, air It is cooled to room temperature under atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.Oxygen as shown in Figure 10 Change antimony -280 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum.Know that gained alloy is antimony oxide and antimony.
Embodiment 4
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (20.65g), antimony source (SbCl3, 0.423g) and carbon source (citric acid, 2.5g) be dissolved in In ionized water (75ml), mixed solution is made in magnetic agitation 6h；
(2) pre-freeze in -10 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -50 DEG C, and then collecting dried object is presoma；
Step 2, it is heat-treated:
Presoma is put into crucible, argon gas is passed through with the flow of 100mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 120mL/min, 600 DEG C are warming up to, cooled to room temperature after 2h is kept the temperature, obtains To intermediate product；
Step 3, drying is washed
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 60 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment
Obtained powder is subjected to secondary heat treatment, 300 DEG C is warming up to the rate of heat addition of 1 DEG C/min, keeps the temperature 4h, air It is cooled to room temperature under atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.Oxygen as shown in figure 11 Change antimony -300 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum.Know that gained alloy is really antimony oxide and antimony.
Embodiment 5
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (22.44g), antimony source (SbCl3, 0.423g) and carbon source (citric acid, 2.5g) be dissolved in In ionized water (75ml), mixed solution is made in magnetic agitation 8h；
(2) pre-freeze in -10 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -46 DEG C, and then collecting dried object is presoma；
Step 2, it is heat-treated:
Presoma is put into crucible, argon gas is passed through with the flow of 130mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 130mL/min, 600 DEG C are warming up to, cooled to room temperature after 2h is kept the temperature, obtains To intermediate product；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 70 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment:
Obtained powder is subjected to secondary heat treatment, 340 DEG C is warming up to the rate of heat addition of 1 DEG C/min, keeps the temperature 4h, air It is cooled to room temperature under atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.Oxygen as shown in figure 12 Change antimony -340 DEG C of antimony alloy composite material secondary heat treatment, 4h XRD spectrum.Know that gained alloy is the antimony oxide of noncrystalline state.
Embodiment 6
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (42.24g), antimony source (SbCl3, 0.32g) and carbon source (citric acid, 5g) be dissolved in from In sub- water (150ml), mixing clear solution is made in magnetic agitation 5h；
(2) pre-freeze in -10 DEG C of refrigerator of mixed solution made from, places into freeze drier after freezing reality completely, Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of -32 DEG C, and then collecting dried object is presoma；
Step 2, it is heat-treated:
Presoma is put into crucible, argon gas is passed through with the flow of 100mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 120mL/min, 750 DEG C are warming up to, cooled to room temperature after 3h is kept the temperature, obtains To intermediate product；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 60 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment:
Obtained powder is subjected to secondary heat treatment, 260 DEG C is warming up to the rate of heat addition of 2 DEG C/min, keeps the temperature 4h, air It is cooled to room temperature under atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.
Embodiment 7
A kind of pyrolysis carbon composite embedding more shell antimony oxide-antimony alloys, the composite material are carbon-coated nanometer Grade antimony oxide-antimony alloy particle is uniformly embedded on pyrolysis carbon structure and is formed, and more shell structurres pass through control heat treatment Time is adjusted with temperature；The antimony oxide-antimony alloy particle diameter is 5~30nm, and carbon coating layer is with a thickness of 1~5nm.
The preparation method of the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys of the invention, including walk as follows It is rapid:
Step 1, presoma is prepared:
(1) by template NaCl (20.64g), antimony source (SbCl3, 0.84g) and carbon source (citric acid, 2.6g) be dissolved in In ionized water (80ml), mixed solution is made in magnetic agitation 8h；
(2) by mixed solution in -5 DEG C of refrigerator pre-freeze, placed into freeze drier after freezing reality completely, -26 Vacuum drying removes moisture removal to keep the cubic structure of NaCl under the conditions of DEG C, and then collecting dried object is presoma；
Step 2, it is heat-treated:
Presoma is put into crucible, argon gas is passed through with the flow of 200mL/min first into tube furnace, to exclude sky Gas, then continue to be passed through inert gas with the flow of 100mL/min, 550 DEG C are warming up to, cooled to room temperature after 3h is kept the temperature, obtains To intermediate product；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；Again Condition by the mixture after washing at 50 DEG C is dried in an oven, obtains powder；
Step 4, secondary heat treatment
Obtained powder is subjected to secondary heat treatment, 270 DEG C is warming up to the rate of heat addition of 5 DEG C/min, keeps the temperature 2h, air It is cooled to room temperature under atmosphere, the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys can be obtained.
By the power relatively of the peak position of XRD antimony oxide and antimony, it can be determined that go out at 240 DEG C, with secondary heat treatment The extension of time, the peak intensity of antimony oxide gradually become by force, and the peak intensity of antimony dies down, and can finally tend to relatively uniform height.This explanation with The extension of heat treatment time, the thickness of antimony outer oxide antimony gradually increase, but antimony can not be oxidized to completely at 240 DEG C Antimony oxide state.With the raising of secondary heat treatment temperature, it has been found that the peak intensity of antimony oxide starts to be better than antimony peak, finally exists Oxidation can be fully achieved at 340 degree simultaneously also as noncrystalline state, i.e. the antimony antimony oxide that is all oxidized to amorphous.When institute When the material of preparation is used for kalium ion battery negative electrode material, discovery chemical property of secondary heat treatment 4h at 240 DEG C is optimal.

Claims (9)

1. a kind of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys, which is characterized in that the material is by carbon-coated Nanoscale antimony-antimony alloy particle and pyrolytic carbon are combined, and carbon-coated nanoscale antimony-antimony alloy particle is uniformly interior In pyrolytic carbon, pyrolytic carbon is the amorphous carbon that carbon source is pyrolyzed formation at 400~800 DEG C；More shells be then by outermost layer carbon, What intermediate oxidation antimony and the inside antimony simple substance formed；The antimony oxide-antimony alloy particle diameter is 5~30nm, carbon coating layer With a thickness of 1~5nm；The cell negative electrode material is in the test of potassium ion half-cell, in 100~5000mA g-1Electric current it is close Under degree, initial charge reversible capacity is 300~650mAh g-1, after 25~100 circulations, capacity is 150~490mAh g-1。
2. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 1 Method, which comprises the steps of:
Step 1, presoma is prepared:
(1) template NaCl, antimony source and carbon source are mixed and is dissolved in deionized water, it is molten that mixing is made in 3~12h of magnetic agitation Liquid；Wherein, the molar ratio of carbon atom is 1:(10~500 in antimony ion contained in antimony source and carbon source), antimony contained in antimony source The molar ratio of ion and NaCl are 1:(100~500)；
(2) mixed solution made from after freezing reality completely, then carries out vacuum freezedrying in -40~-10 DEG C of pre-freezes, -70~- Vacuum freezedrying under the conditions of 10 DEG C, then collecting dried object is presoma；
Step 2, primary heat treatment:
Presoma is put into crucible, is placed in tube furnace is heat-treated in an inert atmosphere, is warming up to 550~750 DEG C, heat preservation 2 Cooled to room temperature after~5h, obtains intermediate product；Inertia is wherein passed through with the flow of 50~500mL/min into tube furnace Gas to exclude air, then with the flow of 50~200mL/min continues to be passed through inert gas；
Step 3, drying is washed:
Intermediate product is taken out from tube furnace, washed, filtered repeatedly with deionized water, until thoroughly removing NaCl；It will wash again Mixture after washing is dried under conditions of 60~80 DEG C, obtains powder；
Step 4, secondary heat treatment:
Powder is subjected to secondary heat treatment, at 200~340 DEG C, heat preservation 1~for 24 hours, it is cooled to room temperature, can obtain under air atmosphere To the pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys.
3. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 1, carbon source is one or more of citric acid, sucrose, glucose, starch, Victoria C；Institute The antimony source stated is one of antimony trichloride, antimony acetate, antimony tartrate or nitric acid antimony.
4. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 1, deionized water dosage >=NaCl solubility, i.e. the complete dissolved clarification of NaCl.
5. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 1, pre-freeze is carried out using refrigerator, the pressure of freeze-drying is≤- 50pa.
6. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 2, heating condition are as follows: using one or more of argon gas or helium as inert gas Source.
7. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 2, the heating rate of heat treatment is 5~10 DEG C/min.
8. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 3, dried using baking oven.
9. a kind of preparation side of pyrolysis carbon composite for embedding more shell antimony oxide-antimony alloys according to claim 2 Method, which is characterized in that in the step 4, heating condition are as follows: under air atmosphere, heating rate is 1~10 DEG C/min.
CN201910670928.3A 2019-07-24 2019-07-24 Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof Active CN110380038B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910670928.3A CN110380038B (en) 2019-07-24 2019-07-24 Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910670928.3A CN110380038B (en) 2019-07-24 2019-07-24 Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110380038A true CN110380038A (en) 2019-10-25
CN110380038B CN110380038B (en) 2020-09-01

Family

ID=68255570

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910670928.3A Active CN110380038B (en) 2019-07-24 2019-07-24 Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110380038B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111477860A (en) * 2020-05-11 2020-07-31 广西师范大学 Preparation method of GaSn/NC composite material
CN112928273A (en) * 2021-01-29 2021-06-08 华南师范大学 Lithium ion battery cathode material and preparation method and application thereof
CN112993225A (en) * 2021-02-06 2021-06-18 长沙理工大学 Antimony-based composite electrode material and preparation method and application thereof
CN113381018A (en) * 2021-04-20 2021-09-10 南昌航空大学 Nitrogen-fluorine atom doped three-dimensional porous carbon electrode material, preparation method and application thereof
CN114373895A (en) * 2021-12-21 2022-04-19 国网内蒙古东部电力有限公司电力科学研究院 Preparation method and application of antimony-sodium alloy electrode
CN115415537A (en) * 2022-08-22 2022-12-02 哈尔滨工业大学（深圳） Preparation method and application of alloy type nano material adopting high-temperature thermal radiation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943837A (en) * 2014-04-11 2014-07-23 浙江大学 Preparation methods of antimony trioxide and antimony trioxide composite material and applications of antimony trioxide and antimony trioxide composite material in sodium-ion batteries
CN106784710A (en) * 2016-12-28 2017-05-31 广东工业大学 A kind of carbon@metal oxide@metals/three-dimensional porous graphene composite material of core shell structure and its preparation method and application
CN108550840A (en) * 2018-05-16 2018-09-18 东北大学秦皇岛分校 Three-dimensional netted carbon embeds antimony-containing alloy kalium ion battery negative material and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103943837A (en) * 2014-04-11 2014-07-23 浙江大学 Preparation methods of antimony trioxide and antimony trioxide composite material and applications of antimony trioxide and antimony trioxide composite material in sodium-ion batteries
CN106784710A (en) * 2016-12-28 2017-05-31 广东工业大学 A kind of carbon@metal oxide@metals/three-dimensional porous graphene composite material of core shell structure and its preparation method and application
CN108550840A (en) * 2018-05-16 2018-09-18 东北大学秦皇岛分校 Three-dimensional netted carbon embeds antimony-containing alloy kalium ion battery negative material and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
N. LI, S. LIAO等: "Uniformly dispersed self-assembled growth of Sb2O3 /Sb@graphene nanocomposites on a 3D carbon sheet network for high Na-storage capacity and excellent stability", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111477860A (en) * 2020-05-11 2020-07-31 广西师范大学 Preparation method of GaSn/NC composite material
CN112928273A (en) * 2021-01-29 2021-06-08 华南师范大学 Lithium ion battery cathode material and preparation method and application thereof
CN112928273B (en) * 2021-01-29 2022-07-26 华南师范大学 Lithium ion battery cathode material and preparation method and application thereof
CN112993225A (en) * 2021-02-06 2021-06-18 长沙理工大学 Antimony-based composite electrode material and preparation method and application thereof
CN112993225B (en) * 2021-02-06 2022-03-08 长沙理工大学 Antimony-based composite electrode material and preparation method and application thereof
CN113381018A (en) * 2021-04-20 2021-09-10 南昌航空大学 Nitrogen-fluorine atom doped three-dimensional porous carbon electrode material, preparation method and application thereof
CN114373895A (en) * 2021-12-21 2022-04-19 国网内蒙古东部电力有限公司电力科学研究院 Preparation method and application of antimony-sodium alloy electrode
CN114373895B (en) * 2021-12-21 2024-01-30 国网内蒙古东部电力有限公司电力科学研究院 Preparation method and application of antimony-sodium alloy electrode
CN115415537A (en) * 2022-08-22 2022-12-02 哈尔滨工业大学（深圳） Preparation method and application of alloy type nano material adopting high-temperature thermal radiation
CN115415537B (en) * 2022-08-22 2023-10-13 哈尔滨工业大学（深圳） Preparation method and application of alloy type nano material adopting high-temperature heat radiation

Also Published As

Publication number Publication date
CN110380038B (en) 2020-09-01

Similar Documents

Publication Publication Date Title
CN110380038A (en) Embed the pyrolysis carbon composite and preparation method of more shell antimony oxide-antimony alloys
CN108615886B (en) Thin-wall porous carbon sphere material, preparation thereof and application of thin-wall porous carbon sphere material as negative electrode material of sodium-ion battery
CN108695498A (en) A kind of porous carbon embeds the cell negative electrode material and preparation method thereof of kamash alloy
CN104752698B (en) A kind of Si-C composite material for negative electrode of lithium ion battery and preparation method thereof
CN107785552B (en) Nitrogen-doped flower-like hierarchical structure porous carbon-selenium composite positive electrode material and preparation method and application thereof
CN106654192B (en) Tin sulfide/graphene sodium-ion battery composite negative electrode material and preparation method thereof
CN108550840A (en) Three-dimensional netted carbon embeds antimony-containing alloy kalium ion battery negative material and preparation method
CN107069001B (en) Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof
CN105470511B (en) The preparation method of tin-cobalt alloy situ catalytic three-dimensional grapheme/tin/carbon nanometer pipe composite material
CN108682833B (en) Preparation method of lithium iron phosphate-based modified cathode material
CN110931775A (en) Modification method of lithium-rich manganese-based positive electrode material
CN103346297A (en) Preparation method for carbon coated composite metal oxide electrode material
CN104993118A (en) Synthesizing method for lithium-ion negative electrode material of Li4Ti5O12/C
CN110391408A (en) A kind of pyrolytic carbon cell negative electrode material of embedded tin-based oxide and preparation method thereof
CN107808955A (en) A kind of absorbent charcoal material with spherical structure and its preparation method and application
CN109755515A (en) A kind of lithium ion battery silicon/anode composite and preparation method thereof
CN106848252A (en) One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery
Feng et al. Se/CNTs microspheres as improved performance for cathodes in Li-Se batteries
WO2022021642A1 (en) Sodium ion battery negative electrode material and preparation method therefor
CN112909246A (en) Bismuth telluride/carbon nanowire composite material and preparation method and application thereof
CN110416501B (en) Electrostatic self-assembly three-dimensional flower-shaped cobalt disulfide/rGO composite material and preparation method and application thereof
CN110510595B (en) Preparation method of N/S co-doped porous carbon for lithium-sulfur battery
CN115763715A (en) Bi x Se y /C composite material, preparation method and application thereof, and method for regulating bismuth-selenium atomic ratio of composite material
CN108987724A (en) A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof
CN109285998B (en) Silicon/silicon iron oxide/ferric oxide/carbon core-shell composite structure material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant