CN104953089A - Preparation method of lithium-sulfur battery positive electrode material based on sulfur filled carbon nano cage - Google Patents
Preparation method of lithium-sulfur battery positive electrode material based on sulfur filled carbon nano cage Download PDFInfo
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/58—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
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- 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
The invention discloses a method of lithium-sulfur battery positive electrode material which is used for constructing high sulfur filling amount by utilizing a carbon nano cage (CNC) as a carrier. The carbon nano cage which has a multi-stage structure, excellent electric conductivity, high pore volume and large specific surface is made by adopting a chemical vapor deposition method is taken as the carrier, the carbon nano cage is filled with sulfur uniformly through a high-temperature melting method, the preparation method is simple and the environment-friendly effect is achieved. Taken as the positive electrode of a lithium-sulfur battery, a compound with high sulfur loading amount shows high specific capacity, high rate capability and high cycle stability.
Description
Technical field
The present invention relates to a kind of preparation of filling the novel high-performance lithium sulfur battery anode material of nano cages (CNC) based on sulphur.
Background technology
Lithium-sulfur cell adopts lithium anode and elemental sulfur positive pole, the high actual energy density (400 ~ 600Wh/kg) that there is very high theoretical energy density (2600Wh/kg) and can expect, and sulphur simple substance aboundresources and cheap, be considered to most potential novel secondary battery (Nat.Mater. after lithium ion battery, 2012,11,19.).But have passed through the research of decades, lithium-sulfur cell large-scale commercial not yet so far, this is mainly due to the insulating properties of active material sulphur and discharging product Li2S, and intermediate product polysulfide dissolves the effect of shuttling back and forth caused, high rate performance (the Acc.Rev.Res. of little active material utilization, short cycle life and difference will be caused, 2013,46,1125; MRS Bulletin, 2011,36,506; Chem.Soc.Rev., 2013,42,3018.).In recent years, large quantifier elimination adopted carbon nanomaterial as mesoporous carbon (Nat.Mater., 2009,8,500; Angew.Chem.Int.Ed., 2011,50,5904.), carbon nano-fiber (Nano Lett., 2011,11,4462; Adv.Mater., 2011,23,5641.), carbon nano-tube (Nano Lett., 2011,11,4288; Chem.Commun., 2012,48,1233.), Graphene (Chem.Commun., 2012,48,1233; J.Am.Chem.Soc., 2011,133,18522.) etc., to increase the conductivity of active material and to reduce the dissolving of polysulfide, thus specific capacity and cycle performance can be greatly improved.But the loading of sulphur is all at below 70wt% in most of compound, the increase of such non-active material will reduce mass energy density and the volume energy density of lithium-sulfur cell.It is generally acknowledged when sulphur loading is more than 80wt%, just can reach the demand (J.Phys.Chem.Lett., 2014,5,882.) of electrode material practical application.The high pore volume material with carbon element of nearest report, obtains the composite material (more than 80wt%) of high-sulfur loading with this, but its specific discharge capacity, cyclical stability and high rate performance all undesirable (Chem.Commun., 2012,48,1233; ACS Appl.Mater.Interfaces, 2013,5,10782; ACS Appl.Mater.Interfaces, 2013,5,2208.).Therefore, find the composite material that not only there is high-sulfur loading but also excellent properties can be obtained, be still the challenge that of current lithium sulfur battery anode material is huge.
The method that we have developed the chemical vapour deposition (CVD) with independent intellectual property right prepares the nano cages (CN200810023448.X) with multilevel hierarchy, excellent conductivity, high pore volume and Large ratio surface.These unique structural feature impart the ability be encapsulated in by high carrying capacity sulphur in carbon cage, thus can reduce the dissolving of polysulfide and strengthen electronic conductivity and ion diffusion rates, and then obtain large specific capacity, long circulating stability and high rate capability.
Summary of the invention
The object of this invention is to provide a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur, this lithium sulfur battery anode material with high-sulfur loading, shows large specific capacity, high high rate performance, long cyclical stability and low cost.
Concrete technical scheme of the present invention is as follows: a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur, and step comprises:
(1) chemical vapour deposition technique prepares CNC carrier: the patent (CN200810023448.X) with independent intellectual property right is asked for an interview in the preparation of CNC.
(2) prepare the carbon-sulfur compound S CNC of high-sulfur loading: the CNC and the sulphur powder that take constant weight ratio, and grinding evenly.Said mixture is put in Muffle furnace, is warmed up to uniform temperature and keeps a period of time, in this process, sulphur is melted and is diffused in nano cages; Again temperature be elevated to uniform temperature and keep a period of time, in this process, to be removed the sulphur on carbon cage surface by distillation mode; Be cooled to room temperature, the S@CNC compound of sulphur loading can be obtained.
It is characterized in that in step (2), CNC can be 700 DEG C.Prepare under 800 DEG C or 900 DEG C of synthesis conditions.
It is characterized in that, in step (2), sulphur powder is sublimed sulfur.
It is characterized in that in step (2), milling time at least 30 minutes.
It is characterized in that, in step (2), the CNC of constant weight ratio and sulphur powder are between 1:1 and 1:12.
It is characterized in that in step (2), be heated to melt, and at least keep 12h.
It is characterized in that in step (2), then warming temperature keep 2h to 250 DEG C.
The use limits of lithium sulfur battery anode material: the weight ratio mixing of obtained active material, acetylene black and Kynoar being pressed 8:1:1, take 1-METHYLPYRROLIDONE as solvent, be applied to equably on aluminium foil after stirring, 80 DEG C of oven dry compressing tablets, obtain work electrode sheet.The loading of active material is at 1.0 ~ 1.5mg/cm-2.Electrolyte is two trifluoromethanesulfonimide lithiums (LiTFSI)/dimethyl ether (DME)-dioxolane (DOL) (the volume ratio 1:1) of 1mol/L, the LiNO3 also containing 1wt%.Barrier film is polypropylene, polyethylene microporous barrier (Celgard2500).All batteries (2032 type button cell) are all assembled in the glove box of anhydrous and oxygen-free, and lithium sheet is as to electrode.NEWARE CT3008 multichannel battery measurement device carries out battery testing, and adopt constant current charge-discharge method, voltage range is 1.7 ~ 2.8V.
Technique effect of the present invention is as follows:
Proposed by the invention prepare high-sulfur carrying capacity and there is the lithium sulfur battery anode material of excellent electrochemical performance, it is characterized in that CNC used has the features such as multilevel hierarchy, excellent conductivity, high pore volume and Large ratio surface.
Proposed by the invention prepare high-sulfur carrying capacity and there is the lithium sulfur battery anode material of excellent electrochemical performance, it is characterized in that preparation process is simple, cost is low, advantages of environment protection.
Proposed by the invention prepare high-sulfur carrying capacity and have the lithium sulfur battery anode material of excellent electrochemical performance, its technical characteristic is that sulphur carrying capacity can up to 50wt% ~ 90wt%; When sulphur carrying capacity is up to 80wt% and the CNC with 800 DEG C of synthesis, this carbon-sulfur compound has the initial specific capacities up to 1095mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can have the specific capacity up to 558mAh/g.
Accompanying drawing explanation
The typical transmission electromicroscopic photograph (TEM) of Fig. 1 support C NC and carbon-sulfur compound S@CNC.
The typical scan electromicroscopic photograph (SEM) of Fig. 2 carbon-sulfur compound S@CNC and Energy Dispersive X spectrogram.
The cyclical stability of Figure 38 0%S@CNC under 1A/g current density and coulombic efficiency, and corresponding voltage curve.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the inventive method is described.
The patent (CN200810023448.X) with independent intellectual property right is asked for an interview in the preparation of CNC.
The preparation of carbon-sulfur compound S@CNC and lithium-sulfur cell performance test
Embodiment 1 is with the CNC of 700 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 50wt%.
Take CNC and the sublimed sulfur powder of 700 DEG C of synthesis of part by weight 1:1, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 50wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1105mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 603mAh/g.
Embodiment 2 is with the CNC of 700 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 67wt%.
Take CNC and the sublimed sulfur powder of 700 DEG C of synthesis of part by weight 1:2, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 67wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1076mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 578mAh/g.
Embodiment 3 is with the CNC of 700 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 5wt%.
Take CNC and the sublimed sulfur powder of 700 DEG C of synthesis of part by weight 1:5, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 80wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1050mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 560mAh/g.
Embodiment 4 is with the CNC of 700 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 90wt%.
Take CNC and the sublimed sulfur powder of 700 DEG C of synthesis of part by weight 1:12, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 90wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 980mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 519mAh/g.
Embodiment 5 is with the CNC of 800 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 80wt%.
Take CNC and the sublimed sulfur powder of 800 DEG C of synthesis of part by weight 1:5, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 80wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1095mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 558mAh/g.
Embodiment 6 is with the CNC of 800 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 50wt%.
Take CNC and the sublimed sulfur powder of 800 DEG C of synthesis of part by weight 1:1, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 83wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1056mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 550mAh/g.
Embodiment 7 is with the CNC of 800 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 75wt%.
Take CNC and the sublimed sulfur powder of 800 DEG C of synthesis of part by weight 1:3, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 75wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1032mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 541mAh/g.
Embodiment 8 is with the CNC of 800 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 90wt%.
Take CNC and the sublimed sulfur powder of 800 DEG C of synthesis of part by weight 1:10, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 90 wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 991mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 526mAh/g.
Embodiment 9 is with the CNC of 900 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 80wt%.
Take CNC and the sublimed sulfur powder of 900 DEG C of synthesis of part by weight 1:5, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 80wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1022mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 546mAh/g.
Embodiment 10 is with the CNC of 900 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 80wt%.
Take CNC and the sublimed sulfur powder of 900 DEG C of synthesis of part by weight 1:4, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 80wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 1003mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 535mAh/g.
Embodiment 11 is with the CNC of 900 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 85wt%.
Take CNC and the sublimed sulfur powder of 900 DEG C of synthesis of part by weight 1:8, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 85wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 994mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 521mAh/g.
Embodiment 12 is with the CNC of 900 DEG C of synthesis for carrier, and preparation load capacity is S@CNC compound and the lithium-sulfur cell performance test of 90wt%.
Take CNC and the sublimed sulfur powder of 900 DEG C of synthesis of part by weight 1:10, mix and grind 30 minutes.Said mixture is put in Muffle furnace, is warmed up to and melts and keep 12h; Again temperature is elevated to 250 DEG C and keeps 2h, be cooled to room temperature, the S@CNC compound that sulphur loading is 90wt% can be obtained.This lithium sulfur battery anode material is loaded 2032 button cells measure, this compound represents the initial specific capacities up to 973mAh/g under the high current density of 1A/g, even if after 300 circle circulations, still can reach the specific capacity of 507mAh/g.
Comparative example 1 with business-like XC-72 for carrier prepares the carbon-sulfur compound and lithium-sulfur cell performance test that loading is 80wt%.Preparation method and appreciation condition are with embodiment 5.Evaluation result is in table 1.
Comparative example 2 with business-like carbon nano-tube (CNT) for carrier prepares the carbon-sulfur compound and lithium-sulfur cell performance test that loading is 80 wt%.Preparation method and appreciation condition are with embodiment 5.Evaluation result is in table 1.
Comparative example 3 with the result of bibliographical information as a comparison (Chem.Commun., 2012,48,1233.).Evaluation result is in table 1.
Comparative example 4 with the result of bibliographical information as a comparison (ACS Appl.Mater.Interfaces, 2013,5,10782.).Evaluation result is in table 1.
Comparative example 5 with the result of bibliographical information as a comparison (ACS Appl.Mater.Interfaces, 2013,5,2208.).Evaluation result is in table 1.
Table 180%S@CNC lithium-sulfur cell Evaluation results.
[a] this patent condition: use 800 DEG C of CNC synthesized.
[b, c] this patent condition: use business-like XC-72 and carbon nano-tube (CNT), preparation method and appreciation condition are with embodiment 5.
[d] document: Chem.Commun., 2012,48,1233.
[e] document: ACS Appl.Mater.Interfaces, 2013,5,10782.
[f] document: ACS Appl.Mater.Interfaces, 2013,5,2208.
Claims (8)
1. fill the preparation of the lithium sulfur battery anode material of nano cages based on sulphur for one kind, step comprises (1), and chemical vapour deposition technique prepares CNC carrier, it is characterized in that: described step also comprises (2) and prepares the carbon-sulfur compound that CNC loads high-load sulphur:
Take CNC and the sulphur powder of constant weight ratio, and grinding evenly, is put in Muffle furnace by above-mentioned CNC and sulphur powder mixture, be warmed up to the first temperature and keep a period of time for the first time, in this process, sulphur melted and is diffused in nano cages; Again temperature be elevated to the second temperature and keep a period of time, in this process, to be removed the sulphur on carbon cage surface by distillation mode for the second time; Be cooled to room temperature, the S@CNC compound of sulphur loading can be obtained.
2., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described sulphur powder is sublimed sulfur.
3., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described milling time at least 30 minutes.
4., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), the proportion of described a certain proportion of CNC and sulphur powder is between 1:1 and 1:10.
5., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described first temperature can be 700 DEG C, 800 DEG C and 900 DEG C of one of them temperature.
6., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described first time keeps a period of time to be at least 12h.
7., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described second temperature is 250 DEG C.
8., according to a kind of preparation of filling the lithium sulfur battery anode material of nano cages based on sulphur according to claim 1, it is characterized in that: in step (2), described second time keeps a period of time to be 2h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390683A (en) * | 2015-12-22 | 2016-03-09 | 苏州大学 | Sulfur-based negative electrode material of lithium ion batteries and application thereof |
| CN105826540A (en) * | 2016-06-03 | 2016-08-03 | 合肥工业大学 | Lithium-sulfur battery composite anode material and preparation method and application thereof |
| CN108400285A (en) * | 2018-03-09 | 2018-08-14 | 南京大学 | A kind of carbon-based no metal elctro-catalyst for promoting polysulfide conversion in lithium-sulfur cell |
| CN108448093A (en) * | 2018-03-21 | 2018-08-24 | 中国计量大学 | A kind of lithium sulfur battery anode material and preparation method thereof of CoS classifying nanos bubble composite sulfur |
| CN108767261A (en) * | 2018-06-13 | 2018-11-06 | 国家纳米科学中心 | A kind of graphitized carbon material, preparation method and the application of three-D micro-nano composite construction |
| CN110165162A (en) * | 2019-04-28 | 2019-08-23 | 南京大学 | A kind of carbon-sulfur compound positive electrode of lithium-sulfur cell |
| CN113346054A (en) * | 2021-04-23 | 2021-09-03 | 西交利物浦大学 | Preparation method and application of MXene-carbon nanocage-sulfur composite material |
| CN113823773A (en) * | 2020-06-19 | 2021-12-21 | 国家纳米科学中心 | Carbon cage material with controllable size and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390683A (en) * | 2015-12-22 | 2016-03-09 | 苏州大学 | Sulfur-based negative electrode material of lithium ion batteries and application thereof |
| CN105826540A (en) * | 2016-06-03 | 2016-08-03 | 合肥工业大学 | Lithium-sulfur battery composite anode material and preparation method and application thereof |
| CN108400285A (en) * | 2018-03-09 | 2018-08-14 | 南京大学 | A kind of carbon-based no metal elctro-catalyst for promoting polysulfide conversion in lithium-sulfur cell |
| CN108448093A (en) * | 2018-03-21 | 2018-08-24 | 中国计量大学 | A kind of lithium sulfur battery anode material and preparation method thereof of CoS classifying nanos bubble composite sulfur |
| CN108448093B (en) * | 2018-03-21 | 2020-09-18 | 中国计量大学 | CoS-graded nano-bubble composite sulfur lithium-sulfur battery positive electrode material and preparation method thereof |
| CN108767261A (en) * | 2018-06-13 | 2018-11-06 | 国家纳米科学中心 | A kind of graphitized carbon material, preparation method and the application of three-D micro-nano composite construction |
| CN108767261B (en) * | 2018-06-13 | 2020-11-20 | 国家纳米科学中心 | Graphitized carbon material with three-dimensional micro-nano composite structure, and preparation method and application thereof |
| CN110165162A (en) * | 2019-04-28 | 2019-08-23 | 南京大学 | A kind of carbon-sulfur compound positive electrode of lithium-sulfur cell |
| CN113823773A (en) * | 2020-06-19 | 2021-12-21 | 国家纳米科学中心 | Carbon cage material with controllable size and preparation method and application thereof |
| CN113346054A (en) * | 2021-04-23 | 2021-09-03 | 西交利物浦大学 | Preparation method and application of MXene-carbon nanocage-sulfur composite material |
| CN113346054B (en) * | 2021-04-23 | 2022-04-08 | 西交利物浦大学 | Preparation method and application of MXene-carbon nanocage-sulfur composite material |
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