CN106058184A - Method for preparing tin dioxide/porous carbon sphere composite material - Google Patents

Method for preparing tin dioxide/porous carbon sphere composite material Download PDF

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CN106058184A
CN106058184A CN201610539100.0A CN201610539100A CN106058184A CN 106058184 A CN106058184 A CN 106058184A CN 201610539100 A CN201610539100 A CN 201610539100A CN 106058184 A CN106058184 A CN 106058184A
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porous carbon
carbon ball
sno
solution
carbon sphere
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孙晓红
李鑫
胡旭东
郑春明
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Tianjin 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
    • 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
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a method for preparing a tin dioxide/porous carbon sphere composite material. The method comprises the steps that a carbon sphere is presintered in an argon atmosphere; the presintered carbon sphere and KOH are ground and mixed to obtain a mixture; the mixture is annealed, and an annealed porous carbon sphere is obtained; the annealed porous carbon sphere is repeatedly washed to be neutral and dried to obtain a porous carbon sphere; a C6H12O6 solution is prepared; SnC14.5H2O is added into the C6H12O6 solution, and a C6H12O6 and SnC14.5H2O mixed solution is prepared; the porous carbon sphere is added into the C6H12O6 and SnC14.5H2O mixed solution, and a precursor mixed solution is obtained; the precursor mixed solution is heated to react in a hydrothermal reaction kettle lining, cooled at room temperature to normal temperature, and the SnO2/porous carbon sphere composite material is obtained. The material has good electrochemical stability, and pulverization and fall off of SnO2 in the electrochemical reaction process are restrained.

Description

A kind of method preparing tin ash/porous carbon ball composite
Technical field
The invention belongs to inorganic nano material synthesis field.In particular it relates to the reaction condition in being tested by change is come Prepare tin ash (SnO2The method of)/porous carbon ball composite.
Background technology
Gradually it is applied to electric automobile along with lithium ion battery, the demand of lithium is greatly increased, and the reserves of lithium are limited, And skewness (being mainly distributed on area, America), this longevity that development and application is stored in electrical network and regenerative resource For life energy-storage battery, it may be possible to a bottleneck problem.It is thus desirable to Development of Novel energy-storage battery.Sodium reserves in the earth's crust are rich Richness, accounts for 2.7%, is the 6th to enrich element, and widely distributed, with low cost, and sodium has the physical chemistry similar to lithium Matter, therefore, development is directed to the sodium-ion battery technology of extensive stored energy application and has great strategic importance.
2013, Guoxiu Wang etc. studied and finds SnO2@MWCNT composite can be as sodium-ion battery negative pole material Since material, negative material SnO2And composite is low with its voltage, specific capacity height, low cost, the advantage such as pollution-free cause The very big concern of scholars.SnO2Theoretical specific capacity be 667mAh/g, it is relative to Na+The electrode potential of/Na is 0.7V, this Make SnO2Negative material can obtain higher energy density.But, owing to there is alloying reaction, SnO2Crystal material Expect to occur the biggest volumetric expansion (about 400%) during sodium ion embeds abjection, occur the efflorescence of active substance with de- Fall, reduce the cyclical stability of battery.Report according to pertinent literature, SnO2Composite can effectively suppress volumetric expansion With the powder of detached of active substance, improve the cyclical stability of battery.SnO2/ porous carbon ball composite is due to porous carbon ball Exist and slow down SnO2Volumetric expansion, suppress SnO2Efflorescence and come off, thus improve SnO2As sodium-ion battery negative pole material The electrochemical stability of material.
Summary of the invention
The present invention uses water heat transfer SnO2/ porous carbon ball composite, wherein SnO2Nanoparticle grows equably On porous carbon ball, porous carbon ball inhibits SnO2Efflorescence and come off, slow down SnO2Volumetric expansion, substantially increase material The stability of material.
The present invention provides a kind of and uses hydro-thermal method to synthesize SnO2The method of/porous carbon ball composite.Test also by Change reaction precursor substrate concentration and synthesize SnO2/ porous carbon ball composite.
Technical scheme is as follows:
A kind of method preparing tin ash/porous carbon ball composite；Specifically comprise the following steps that
1). take carbon ball in argon gas atmosphere, carry out preheating；
2). pre-burning carbon ball and KOH ground and mixed are obtained mixture；
3). mixture is made annealing treatment, porous carbon ball after being annealed；
4). porous carbon ball after annealing is washed to neutrality repeatedly, and is dried to obtain porous carbon ball；
5). prepare the C of 0.4-0.6mol/L under magneton stirring condition6H12O6Solution；
6). by SnCl4·5H2O adds step 5) C6H12O6In solution, magneton stirs, preparation 0.25-1.00mol/L's SnCl4·5H2O solution, obtains C6H12O6And SnCl4·5H2The mixed solution of O；
7). by step 4) in the porous carbon ball that obtains add step 6) C that obtains6H12O6And SnCl4·5H2The mixing of O is molten In liquid, magneton stirs, and obtains presoma mixed liquor；
8). presoma mixed liquor is transferred in politef hydrothermal reaction kettle liner, and use stainless steel cauldron After sealing, it is heated to 170-190 DEG C, is incubated 12-36h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol respectively, Obtain SnO2/ porous carbon ball composite.
Described step 1) in carbon ball size preferably smaller than equal to 800nm.
Described step 1) at pre-burning preferably the condition of managing be heating rate be 5-10 DEG C/min, at 450-500 DEG C, be incubated 60- 100min, then naturally cools to room temperature.
Described step 2), the mass ratio of pre-burning carbon ball and KOH is preferably 1:2-1:5.
Described step 3) make annealing treatment condition preferably: in argon gas atmosphere, heating rate is 5-10 DEG C/min, at 600- It is incubated 120-200min at 650 DEG C, then naturally cools to room temperature.
Described step 4) preferably drying condition is to be dried 8-12h at 60-80 DEG C.
Described step 9) by deionized water and preferred 3-5 time of washing with alcohol.
Described with magneton stirring optimum condition be: 1-20r/s.
The invention provides a kind of use water heat transfer SnO2The method of/porous carbon ball composite.Specifically, pass through Preparing porous carbon ball, during Hydrothermal Synthesis, porous carbon spherical macrospore is SnO2Nucleation provides activity position, SnO2Many Carry out nucleating growth on the carbon ball of hole, thus inhibit SnO2Efflorescence in electrochemical reaction process and coming off.
The effect of the present invention is: by hydro-thermal method, synthesized SnO2/ porous carbon ball composite.This material is by SnO2Nanometer Particle becomes with porous carbon set of balls, wherein SnO2Nanoparticle is grown in the upper of porous carbon ball equably, it is suppressed that SnO2In electrochemistry Efflorescence in course of reaction and coming off.
Accompanying drawing explanation
Fig. 1 be embodiment 1 (under), embodiment 2 (in) and embodiment 3 (on) prepared by SnO2/ porous carbon ball composite X-ray diffractogram, the product prepared by explanation is the SnO of complete crystallization2。
SnO prepared by Fig. 2 embodiment 12The SEM figure of/porous carbon ball composite, as it can be seen, product is by porous carbon Ball and SnO2Nano-particle forms, and the size of porous carbon ball is about 500nm, SnO2Nanoparticle size is distributed in 20 50nm Between, the aperture on surface is about 10nm.SnO2Nano-particle is grown in equably on porous carbon ball and forms loose structure, and this can To suppress SnO2Volumetric expansion in charge and discharge process, thus improve the electrochemical cycle stability of material.
Fig. 3 is the SnO of embodiment 3 synthesis2/ porous carbon ball composite SEM figure, it can be seen that product by Porous carbon ball and SnO2Nano-particle forms, and the size of porous carbon ball is about 500nm, SnO2Nanoparticle size is distributed in Between 20 50nm, the aperture on surface is about 10nm.
Fig. 4 is the SnO prepared by embodiment 22The electricity that/porous carbon ball composite is tested after being assembled into battery as negative pole Chemical cycle stability figure, as can be seen from Fig., after battery carries out constant current charge-discharge 20 circle under 50mA/g electric current density (the One circle activation is disregarded), the specific capacity of battery is almost without decay, and the coulombic efficiency of discharge and recharge weekly is all higher than 100%.This SnO is described2/ porous carbon ball composite has good electrochemical cycle stability.
Detailed description of the invention
The method of the embodiment of the present invention, is described by preferred embodiment, and person skilled substantially can be not In departing from present invention, spirit and scope, methods and techniques described herein route is modified or reconfigures, come real The most final technology of preparing.Special needs to be pointed out is, all similar replacements and change are for a person skilled in the art Being apparent from, they are considered as being included in present invention spirit, scope and content.
1). take and be smaller in size than the carbon ball of 800nm and carry out preheating；In argon gas atmosphere, heating rate is 5-10 DEG C/ Min, is incubated 60-100min at 450-500 DEG C, then naturally cools to room temperature；
2). by step 1) the pre-burning carbon ball that obtains and KOH ground and mixed, the mass ratio of pre-burning carbon ball and KOH is 1:2-1: 5；
3). by step 2) the pre-burning carbon ball that obtains makes annealing treatment with the mixture of KOH；In argon gas atmosphere, heat up Speed is 5-10 DEG C/min, is incubated 120-200min, then naturally cools to room temperature at 600-650 DEG C；
4). to step 3) the porous carbon ball that obtains repeatedly is washed to neutrality, and is dried 8-12h at 60-80 DEG C, To porous carbon ball；
5). by C6H12O6Add in deionized water, the C of preparation 0.4-0.6mol/L6H12O6Solution, during with magneton Stirring；
6). by SnCl4·5H2O adds step 5) C that obtains6H12O6In solution, preparation 0.25-1.00mol/L's SnCl4·5H2O solution, during with magneton stir (1-20r/s), obtain C6H12O6And SnCl4·5H2The mixed solution of O；
7). by step 4) in the porous carbon ball that obtains add step 6) C that obtains6H12O6And SnCl4·5H2The mixing of O is molten In liquid, magneton stirs, and obtains presoma mixed liquor；
8). above-mentioned presoma mixed liquor is transferred in politef hydrothermal reaction kettle liner, and uses rustless steel anti- After answering still to seal, it is heated to 170-190 DEG C, is incubated 12-36h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol respectively 3-5 time, obtain SnO2/ porous carbon ball composite.
Embodiment 1:
1). take 1g and be smaller in size than the carbon ball of 800nm in argon gas atmosphere, carry out preheating, heating rate be set to 5 DEG C/ Min, naturally cools to room temperature after being incubated 100min at 450 DEG C；
2). the pre-burning carbon ball 0.3459g that step 1 is obtained and 0.6918g KOH ground and mixed；
3). step 2 being obtained milled mixtures and makes annealing treatment under an argon atmosphere, heating rate is set to 5 DEG C/min, Room temperature is naturally cooled to after being incubated 200min at 600 DEG C；
4). make to be washed with deionized step 3 product 6 times, 60 DEG C of dry 12h, obtain porous carbon ball；
5). by 0.04mol C6H12O6Joining in 100mL deionized water, magneton is uniformly mixed；
6). by the SnCl of 0.025mol4·5H2O adds the C that step 5 obtains6H12O6In solution, magneton stirring mixing is all Even；
7). porous carbon ball 0.3g step 4 obtained adds in above-mentioned mixed solution, and magneton stirs；
8). take the precursor solution that appropriate step 7 obtains and transfer to the politef hydrothermal reaction kettle that capacity is 100mL In liner, stainless steel cauldron seals, and uses baking oven for heating, is heated to 170 DEG C, is incubated 36h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol 3 respectively Secondary, 60 DEG C of dry 12h, obtain SnO2/ porous carbon ball composite.
As it is shown in figure 1, product is the SnO of complete crystallization2Pure phase.Fig. 2 SEM result shows, product by porous carbon ball and SnO2Nano-particle forms, and the size of porous carbon ball is about 500nm, SnO2Nanoparticle size be distributed in 20 50nm it Between, the aperture on surface is about 10nm.SnO2Nano-particle is grown in equably on porous carbon ball and forms loose structure, and this is permissible Suppression SnO2Volumetric expansion in charge and discharge process, thus improve the electrochemical cycle stability of material.
Embodiment 2:
1). take 1g and be smaller in size than the carbon ball of 800nm in argon gas atmosphere, carry out preheating, heating rate be set to 8 DEG C/ Min, naturally cools to room temperature after being incubated 80min at 475 DEG C；
2). the pre-burning carbon ball 0.3002g that step 1 is obtained and 1.0507g KOH ground and mixed；
3). step 2 being obtained milled mixtures and makes annealing treatment under an argon atmosphere, heating rate is set to 8 DEG C/min, Room temperature is naturally cooled to after being incubated 160min at 625 DEG C；
4). make to be washed with deionized step 3 product 8 times, 70 DEG C of dry 10h, obtain porous carbon ball；
5). by 0.05mol C6H12O6Joining in 100mL deionized water, magneton is uniformly mixed；
6). by the SnCl of 0.05mol4·5H2O adds the C that step 5 obtains6H12O6In solution, magneton is uniformly mixed；
7). porous carbon ball 0.3g step 4 obtained adds in above-mentioned mixed solution, and magneton stirs；
8). take the precursor solution that appropriate step 7 obtains and transfer to the politef hydrothermal reaction kettle that capacity is 100mL In liner, stainless steel cauldron seals, and uses baking oven for heating, is heated to 180 DEG C, is incubated 24h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol 4 respectively Secondary, 70 DEG C of dry 10h, obtain SnO2/ porous carbon ball composite.
As it is shown in figure 1, product is the SnO of complete crystallization2, do not have other impurity to generate mutually.Fig. 4 electrochemical cycle stability Can figure result show, SnO2The electrochemical cycle stability that/porous carbon ball composite is tested after being assembled into battery as negative pole, After battery carries out constant current charge-discharge 20 circle under 50mA/g electric current density (first lap activates and disregards), the specific capacity of battery does not almost have There is decay, and the coulombic efficiency of discharge and recharge weekly is all higher than 100%.This illustrates SnO2/ porous carbon ball composite has good Good electrochemical cycle stability.
Embodiment 3:
1). take 1g and be smaller in size than the carbon ball of 800nm in argon gas atmosphere, carry out preheating, heating rate be set to 10 DEG C/ Min, naturally cools to room temperature after being incubated 60min at 500 DEG C；
2). the pre-burning carbon ball 0.3015g that step 1 is obtained and 1.5075g KOH ground and mixed；
3). step 2 is obtained milled mixtures and makes annealing treatment under an argon atmosphere, heating rate be set to 10 DEG C/ Min, naturally cools to room temperature after being incubated 120min at 650 DEG C；
4). make to be washed with deionized step 3 product 10 times, 80 DEG C of dry 8h, obtain porous carbon ball；
5). by 0.06mol C6H12O6Joining in 100mL deionized water, magneton is uniformly mixed；
6). by the SnCl of 0.1mol4·5H2O adds the C that step 5 obtains6H12O6In solution, magneton is uniformly mixed；
7). porous carbon ball 0.3g step 4 obtained adds in above-mentioned mixed solution, and magneton stirs；
8). take the precursor solution that appropriate step 7 obtains and transfer to the politef hydrothermal reaction kettle that capacity is 100mL In liner, stainless steel cauldron seals, and uses baking oven for heating, is heated to 190 DEG C, is incubated 12h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol 5 respectively Secondary, 80 DEG C of dry 8h, obtain SnO2/ porous carbon ball composite.
As it is shown in figure 1, product is the SnO of complete crystallization2, do not have other impurity to generate mutually.
To sum up the accompanying drawing of embodiment can clearly be found out, by the present invention in that with water heat transfer SnO2/ porous carbon ball multiple Condensation material, this material is become with porous carbon set of balls by SnO2 nanoparticle, and wherein SnO2 nanoparticle is grown in porous carbon equably The inside of ball, porous carbon ball inhibits SnO2 efflorescence in electrochemical reaction process and comes off.And material when as sodium from During sub-battery cathode, there is preferable electrochemical stability.

Claims (8)

1. the method preparing tin ash/porous carbon ball composite；It is characterized in that specifically comprising the following steps that
1). take carbon ball in argon gas atmosphere, carry out preheating；
2). pre-burning carbon ball and KOH ground and mixed are obtained mixture；
3). mixture is made annealing treatment, porous carbon ball after being annealed；
4). porous carbon ball after annealing is washed to neutrality repeatedly, and is dried to obtain porous carbon ball；
5). prepare the C of 0.4-0.6mol/L under magneton stirring condition6H12O6Solution；
6). by SnCl4·5H2O adds step 5) C6H12O6In solution, magneton stirs, preparation 0.25-1.00mol/L's SnCl4·5H2O solution, obtains C6H12O6And SnCl4·5H2The mixed solution of O；
7). by step 4) in the porous carbon ball that obtains add step 6) C that obtains6H12O6And SnCl4·5H2The mixed solution of O In, magneton stirs, and obtains presoma mixed liquor；
8). presoma mixed liquor is transferred in politef hydrothermal reaction kettle liner, and use stainless steel cauldron to seal After, it is heated to 170-190 DEG C, is incubated 12-36h；
9). after reaction terminates, under room temperature, it is cooled to room temperature, takes out reactant, use deionized water and washing with alcohol respectively, obtain SnO2/ porous carbon ball composite.
2. the method for claim 1, is characterized in that described step 1) in carbon ball be smaller in size than equal to 800nm.
3. the method for claim 1, is characterized in that described step 1) preheating condition be heating rate be 5-10 DEG C/ Min, is incubated 60-100min at 450-500 DEG C, then naturally cools to room temperature.
4. the method for claim 1, is characterized in that described step 2), the mass ratio of pre-burning carbon ball and KOH is 1:2-1: 5。
5. the method for claim 1, is characterized in that described step 3) annealing condition is: in argon gas atmosphere, rises Temperature speed is 5-10 DEG C/min, is incubated 120-200min, then naturally cools to room temperature at 600-650 DEG C.
6. the method for claim 1, is characterized in that described step 4) drying condition be at 60-80 DEG C be dried 8-12h.
7. the method for claim 1, is characterized in that described step 9) by deionized water and washing with alcohol 3-5 time.
8. the method for claim 1, it is characterized in that described with magneton stirring condition be: 1-20r/s.
CN201610539100.0A 2016-07-08 2016-07-08 Method for preparing tin dioxide/porous carbon sphere composite material Pending CN106058184A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784699A (en) * 2016-12-26 2017-05-31 天津大学 A kind of method for preparing the composite for adhering to tin oxide nano particles on honeycomb carbon
CN107132254A (en) * 2017-06-22 2017-09-05 云南大学 A kind of high sensitivity CO gas sensitive material and preparation method and application
CN110600695A (en) * 2019-09-06 2019-12-20 扬州大学 Yolk-eggshell structure tin @ hollow mesoporous carbon sphere material and preparation method thereof
CN112018360A (en) * 2020-08-26 2020-12-01 合肥国轩高科动力能源有限公司 Lithium ion battery cathode material, preparation method thereof and lithium ion battery
CN112038614A (en) * 2020-09-22 2020-12-04 四川轻化工大学 Negative electrode material for sodium ion battery and preparation method thereof
CN113745491A (en) * 2021-08-10 2021-12-03 扬州大学 SnO with double-wall hollow sphere structure2@ C material and preparation method thereof

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CN104157876A (en) * 2014-08-14 2014-11-19 上海交通大学 Preparation method of porous carbon-tin nanocomposite material for lithium battery cathode

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CN104157876A (en) * 2014-08-14 2014-11-19 上海交通大学 Preparation method of porous carbon-tin nanocomposite material for lithium battery cathode

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784699A (en) * 2016-12-26 2017-05-31 天津大学 A kind of method for preparing the composite for adhering to tin oxide nano particles on honeycomb carbon
CN107132254A (en) * 2017-06-22 2017-09-05 云南大学 A kind of high sensitivity CO gas sensitive material and preparation method and application
CN107132254B (en) * 2017-06-22 2019-10-29 云南大学 A kind of high sensitivity CO gas sensitive material and the preparation method and application thereof
CN110600695A (en) * 2019-09-06 2019-12-20 扬州大学 Yolk-eggshell structure tin @ hollow mesoporous carbon sphere material and preparation method thereof
CN110600695B (en) * 2019-09-06 2023-07-18 扬州大学 Yolk-eggshell structure tin@hollow mesoporous carbon sphere material and preparation method thereof
CN112018360A (en) * 2020-08-26 2020-12-01 合肥国轩高科动力能源有限公司 Lithium ion battery cathode material, preparation method thereof and lithium ion battery
CN112038614A (en) * 2020-09-22 2020-12-04 四川轻化工大学 Negative electrode material for sodium ion battery and preparation method thereof
CN113745491A (en) * 2021-08-10 2021-12-03 扬州大学 SnO with double-wall hollow sphere structure2@ C material and preparation method thereof
CN113745491B (en) * 2021-08-10 2022-11-29 扬州大学 SnO with double-wall hollow ball structure 2 @ C material and preparation method thereof

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