CN104600296A - Preparation method of Se-C positive electrode composite material of lithium-selenium battery - Google Patents
Preparation method of Se-C positive electrode composite material of lithium-selenium battery Download PDFInfo
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- CN104600296A CN104600296A CN201410848164.XA CN201410848164A CN104600296A CN 104600296 A CN104600296 A CN 104600296A CN 201410848164 A CN201410848164 A CN 201410848164A CN 104600296 A CN104600296 A CN 104600296A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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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- 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
The invention specifically relates to a preparation method of a Se-C positive electrode composite material of a lithium-selenium battery. The preparation method comprises the following steps: firstly, putting selenium and carbon materials into a ball mill and mixing by ball milling, and then putting the mixture into a microwave furnace for microwave heating compounding to prepare the Se-C positive electrode microwave composite material high in dispersion uniformity. The carbon material utilized in the preparation method is a material subjected to commercial quantity production and is low in cost; meanwhile, according to the microwave heating compounding method, the operation process is simple, the energy consumption is low and the yield is high; the product is relatively high in performance consistency, and can be produced continuously and applied commercially.
Description
(1) technical field
The invention belongs to field of electrochemical batteries, be specifically related to a kind of preparation method of lithium selenium cell Se-C anode composite material.
(2) background technology
The theoretical specific energy of lithium-sulfur cell reaches 2600Wh/kg, far above the common positive electrode LiCoO of lithium ion battery
2, LiMnO
2, LiFePO
4capacity.In addition, it is high that lithium-sulfur cell has specific capacity, pollution-free, aboundresources and the advantages such as low price.So sulphur is a kind of serondary lithium battery active material had a great attraction, and especially has good application prospect in power vehicle direction.But, be limited to the insulating properties of sulphur and discharging product lithium sulfide thereof, and a series of many lithium sulfides intermediate products formed in charge and discharge process are soluble in the characteristics such as electrolyte, it is on the low side that lithium-sulfur cell also exists sulphur positive pole utilance, the shortcomings such as cycle performance difference, are thus difficult to actual utilization.
Selenium, as the congeners of sulphur, is expected to the positive electrode becoming a kind of great potential.Although the specific discharge capacity of selenium is 675 mAh/g, lower than sulphur (1675 mAh/g), but the density of selenium is about 2.5 times of sulphur, so the volume and capacity ratio of selenium (3253 mAh/cm
3) and sulphur (3467 mAh/cm
3) be more or less the same.High (the Se 10 of Conductivity Ratio sulphur of selenium
-5scm
-1, S 10
-30scm
-1), the electrochemical reaction of carrying out on lithium sheet surface is rapider, and stock utilization is high.In addition. the effect of shuttling back and forth of selenium is low.Various mesoporous carbon and additive etc. are applied to and weaken sulphur positive pole and to shuttle back and forth the measure of effect, are applicable to selenium too.
Lithium-selenium cell, positive pole adopts elemental selenium or selenium-containing compound, and negative pole is lithium metal or lithium alloy, by the fracture of Se-Se key and the mode of generation, carries out the transformation of electric energy and chemical energy.People (the J.Am.Chem.Soc.2012 such as U.S. Argonne National Laboratory Amine, 134,4505-4508) compound is carried out to Se material and the process of carbon nano-tube melting heat, surprised discovery using selenium (Se) as the lithium battery of positive pole and sode cell at room temperature working properly, and normal discharge and recharge 100 times under 4.6V charge cutoff voltage.Above method, various nano-carbon material and elemental selenium is utilized to carry out fusion method compound, improve the discharge capacity of first tens times to a certain extent, but overall cycle performance is still not good, and the complexity of nano-carbon material manufacture method and expensive, recombination time longer (>=8h), make the practical of lithium-sulfur cell also have a segment distance, also need continuous improvement.
(3) summary of the invention
The invention provides a kind of preparation method of lithium selenium cell Se-C anode composite material, utilize the strong wave absorbtion of material with carbon element and quick, the high efficiency of microwave heating method, synthesis has the Se-C composite material of high homogeneity and stability; Further, the good electronic transmission performance that material with carbon element itself has, effectively make up sulphur as positive electrode can not conductivity.Simultaneously, the hole had due to material with carbon element itself can effectively adsorb and hold selenium, suppress the dissolving of discharging product and the migration to negative pole, reduce self discharge and polysulfide ions to shuttle back and forth effect, avoid the non-conductive product when discharge and recharge to become more and more thick insulating barrier in carbon granules outside deposition, thus extend cycle life.And preparation method is simple, raw material is easy to get, and is applicable to large-scale production, possesses very high practical value.
The present invention is achieved through the following technical solutions:
A preparation method for lithium selenium cell Se-C anode composite material, its special character is: comprise the following steps:
(1) selenium powder and material with carbon element are put into ball mill for dry grinding to mix;
(2) Se-C mixed powder good for ball milling is put into microwave oven, after being vacuumized by microwave oven body, pass into protection gas, be heated to the melt temperature of selenium, insulation, obtained Se-C microwave composite material;
(3) by obtained Se-C microwave composite material and conductive agent ground and mixed evenly after, then with binding agent dispersion in a solvent, stirring, makes slurry;
(4) slurry modulated evenly is coated in current collector foil, obtained Se-C anode composite material pole piece after vacuumize.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, in step (1), the mass ratio of selenium and material with carbon element is 1.5 ~ 4:1.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, in step (1), described material with carbon element is at least one in acetylene black, Ketjen black or BP2000.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, in step (1), Ball-milling Time is 2 ~ 12h, and ball milling speed is 200 ~ 500r/min.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, the microwave-oven-heating temperature described in step (2) is 230 DEG C ~ 400 DEG C; Heating rate is 10 ~ 26 DEG C/min; Temperature retention time is 10 ~ 60min; The microwave output power of microwave oven is 0.5 ~ 3kW; Protection gas is argon gas or nitrogen.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, in step (3), the mass ratio of Se-C microwave composite material, conductive agent and binding agent is 7:(1 ~ 2): (1 ~ 2).
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, in step (3), described solvent is 1-METHYLPYRROLIDONE or deionized water; The addition of solvent is for dissolving raw material, and conductive agent is acetylene black, Ketjen black, at least one in BP2000; Binding agent is the aqueous dispersions (LA133) of Kynoar (PVDF) or acrylonitrile multiple copolymer.
The preparation method of lithium selenium cell Se-C anode composite material of the present invention, the collector described in step (4) is aluminium foil; Vacuumize temperature is 50 ~ 80 DEG C, and drying time is 8 ~ 14h.
By the Se-C microwave composite material obtained by such scheme, through thermogravimetric analysis test, wherein Se content is between 45%-70%wt, effectively ensures the content of active material in positive electrode.
Beneficial effect: the preparation method of a kind of lithium selenium cell Se-C anode composite material of the present invention is microwave heating method, because the thermal effect of microwave and non-thermal effect affect the carrying out of chemical reaction simultaneously, under the effect of its thermal effect, Se can reach melt temperature very fast, and sintering time is short.Due to the strong absorbing property of material with carbon element, strong molecular heat vibrate make selenium molecule more traditional heat trnasfer like heating means, selenium can be made better to enter in the hole of carbon and accomplish good filling, making carbon can coated selenium well.And the molecular heat vibration in addition of the mobility of melting selenium, selenium carbon may be made to be more evenly distributed, and self-control forms a best selenium carbon mixed form, and its structure is more stable, has stronger cycle performance.The material with carbon element used in this invention is commercial production formed material, and price is low, can realize continuous prodution, and operating procedure is simple, and power consumption less, productive rate is high, and properties of product consistency is higher.
(4) accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 product;
Fig. 2 is the SEM figure of the Se-C microwave composite material prepared by the embodiment of the present invention 1;
Fig. 3 is the Se element Surface scan figure of the product prepared by the embodiment of the present invention 1;
Fig. 4 is the C element Surface scan figure of the product prepared by the embodiment of the present invention 1;
Fig. 5 is the embodiment of the present invention 1 product charging and discharging curve under 0.2C multiplying power;
Fig. 6 is the cycle electric performance curve of the embodiment of the present invention 1 product under 0.2C and 1C multiplying power;
Fig. 7 is the cycle performance curve of the embodiment of the present invention 2 product under 0.5C multiplying power.
(5) embodiment
Embodiment 1:
Take 2.1g selenium powder and 0.9g Ketjen black respectively, with the rotating speed ball milling 2h of 400r/min on ball mill, obtain the Se-C mixed powder mixed.Again the Se-C mixed powder crossed through ball milling is put into microwave oven, pass into argon gas after vacuumizing, heating rate is 10 DEG C/min, and in 400 DEG C of insulation 1h, microwave output power is 1.0kW, obtains the Se-C microwave composite material that Se content is 55.68wt%.Take 1-METHYLPYRROLIDONE as solvent, obtained Se-C microwave composite material and acetylene black, PVDF are sized mixing with mass ratio 7:1:2.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 60 DEG C of insulation 12h.Fig. 1 is the XRD figure of gained sample, and as seen from the figure, after microwave thermal compound, compound presents unformed state, and the characteristic peak of all Se disappears, and illustrates that Se has well been distributed in Ketjen black Ketjen black matrix, presents unformed shape.Fig. 2 is scanning electron microscope (SEM) photograph and the Surface scan figure of gained sample, and as seen from the figure, in Se-C microwave composite material, Se, C distribute very evenly.With this material for positive pole, metal lithium sheet does the button simulated battery of the lithium selenium cell that negative pole is assembled into.Fig. 3 is the charging and discharging curve of this lithium selenium cell under 0.2C multiplying power, and discharge capacity is 700mAh/g first.Fig. 4 is the cycle performance of described lithium selenium cell respectively under 0.2C, 1C multiplying power.Under 0.2C multiplying power after 100 circulations, reversible discharge specific capacity is still up to 300 mAh/g, and capacity attenuation is mild.Discharge first 542 mAh/g under 1C high magnification, and after 100 circulations, specific discharge capacity is 180 mAh/g, and effect of shuttling back and forth obviously is suppressed.
Embodiment 2:
Take 2.4g selenium powder and 0.6g acetylene black respectively, at ball mill with the rotating speed ball milling 4h of 500r/min, obtain the Se-C mixed powder mixed.Be placed in microwave oven by the Se-C mixed powder crossed through ball milling again, pass into argon gas after vacuumizing, heating rate is 15 DEG C/min, and in 300 DEG C of insulation 50min, microwave output power is 0.8kW, obtains the Se-C microwave composite material that Se content is 61.32wt%.Take deionized water as solvent, obtained Se-C microwave composite material and Ketjen black conductive carbon black, LA133 are sized mixing with mass ratio 7:2:1.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 70 DEG C of insulation 10h.With this material for positive pole, metal lithium sheet is done negative pole and is assembled into button simulated battery, through electric performance test, its under 0.5C multiplying power after 80 cycle charge-discharges capacity still can reach 245 mAh/g.
Embodiment 3:
Take 1.8g selenium powder and 1.2g BP2000 conductive carbon black respectively, with the rotating speed ball milling 5h of 300r/min on ball mill, obtain the Se-C mixed powder mixed.Be placed in microwave oven by the Se-C mixed powder through ball milling again, pass into nitrogen after vacuumizing, heating rate is 25 DEG C/min, and in 350 DEG C of insulation 40min, microwave output power is 0.9kW, obtains the Se-C microwave composite material that Se content is 48.96wt%.Take 1-METHYLPYRROLIDONE as solvent, obtained Se-C microwave composite material, BP2000 conductive carbon black and PVDF are sized mixing with mass ratio 7:1.5:1.5.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 80 DEG C of insulation 8h.With this material for positive pole, metal lithium sheet is done negative pole and is assembled into button simulated battery, through electric performance test, its under 0.1C multiplying power after 100 cycle charge-discharges capacity still can reach 344 mAh/g.
Embodiment 4:
Take 2.4g selenium powder and 0.6g acetylene black respectively, at ball mill with the rotating speed ball milling 12h of 200r/min, obtain the Se-C mixed powder mixed.Be placed in microwave oven by the Se-C mixed powder crossed through ball milling again, pass into argon gas after vacuumizing, heating rate is 26 DEG C/min, and in 400 DEG C of insulation 10min, microwave output power is 3kW, obtains the Se-C microwave composite material that Se content is 45wt%.Take deionized water as solvent, obtained Se-C microwave composite material and Ketjen black conductive carbon black, LA133 are sized mixing with mass ratio 7:1.5:2.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 50 DEG C of insulation 14h.With this material for positive pole, metal lithium sheet is done negative pole and is assembled into button simulated battery, through electric performance test, its under 0.5C multiplying power after 80 cycle charge-discharges capacity still can reach 229 mAh/g.
Embodiment 5:
Take 2.1g selenium powder and 0.9g BP2000 respectively, with the rotating speed ball milling 2h of 300r/min on ball mill, obtain the Se-C mixed powder mixed.Again the Se-C mixed powder crossed through ball milling is put into microwave oven, pass into nitrogen after vacuumizing, heating rate is 18 DEG C/min, and in 370 DEG C of insulation 40min, microwave output power is 0.5kW, obtains the Se-C microwave composite material that Se content is 55.41wt%.Take 1-METHYLPYRROLIDONE as solvent, obtained Se-C microwave composite material and acetylene black, PVDF are sized mixing with mass ratio 7:1:1.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 60 DEG C of insulation 12h.Discharge first 538 mAh/g under 1C high magnification, and after 100 circulations, specific discharge capacity is 185 mAh/g.
Embodiment 6:
Take 5g selenium powder and 0.6g acetylene black respectively, at ball mill with the rotating speed ball milling 4h of 500r/min, obtain the Se-C mixed powder mixed.Be placed in microwave oven by the Se-C mixed powder crossed through ball milling again, pass into argon gas after vacuumizing, heating rate is 15 DEG C/min, and in 230 DEG C of insulation 50min, microwave output power is 0.8kW, and obtaining Se content is 70wt%Se-C microwave composite material.Take deionized water as solvent, obtained Se-C microwave composite material and Ketjen black conductive carbon black, LA133 are sized mixing with mass ratio 7:1.5:1.Finally the slurry mixed up is evenly coated on aluminium foil, and is placed in vacuum drying chamber in 70 DEG C of insulation 10h.With this material for positive pole, metal lithium sheet is done negative pole and is assembled into button simulated battery, through electric performance test, its under 0.5C multiplying power after 200 cycle charge-discharges capacity still can reach 287mAh/g.
Claims (8)
1. a preparation method for lithium selenium cell Se-C anode composite material, is characterized in that: comprise the following steps:
(1) selenium powder and material with carbon element are put into ball mill for dry grinding to mix;
(2) Se-C mixed powder good for ball milling is put into microwave oven, after being vacuumized by microwave oven body, pass into protection gas, be heated to the melt temperature of selenium, insulation, obtained Se-C microwave composite material;
(3) by obtained Se-C microwave composite material and conductive agent ground and mixed evenly after, then with binding agent dispersion in a solvent, stirring, makes slurry;
(4) slurry modulated evenly is coated in current collector foil, obtained Se-C anode composite material pole piece after vacuumize.
2. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1, is characterized in that: in step (1), and the mass ratio of selenium and material with carbon element is 1.5 ~ 4:1.
3. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, is characterized in that: in step (1), and described material with carbon element is at least one in acetylene black, Ketjen black or BP2000.
4. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, is characterized in that: in step (1), Ball-milling Time is 2 ~ 12h, and ball milling speed is 200 ~ 500r/min.
5. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, is characterized in that: the microwave-oven-heating temperature described in step (2) is 230 DEG C ~ 400 DEG C; Heating rate is 10 ~ 26 DEG C/min; Temperature retention time is 10 ~ 60min; The microwave output power of microwave oven is 0.5 ~ 3kW; Protection gas is argon gas or nitrogen.
6. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, it is characterized in that: in step (3), the mass ratio of Se-C microwave composite material, conductive agent and binding agent is 7:(1 ~ 2): (1 ~ 2).
7. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, it is characterized in that: in step (3), described solvent is 1-METHYLPYRROLIDONE or deionized water; The addition of solvent is for dissolving raw material, and conductive agent is acetylene black, Ketjen black, at least one in BP2000; Binding agent is the aqueous dispersions of Kynoar or acrylonitrile multiple copolymer.
8. the preparation method of lithium selenium cell Se-C anode composite material according to claim 1 and 2, is characterized in that: the collector described in step (4) is aluminium foil; Vacuumize temperature is 50 ~ 80 DEG C, and drying time is 8 ~ 14h.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789623A (en) * | 2016-04-17 | 2016-07-20 | 中国计量大学 | Preparation device for selenium/carbon composite electrode material and control method |
| CN106935842A (en) * | 2017-03-08 | 2017-07-07 | 广东工业大学 | Electroplate plating solution, lithium selenium cell positive electrode and the lithium selenium cell of selenium |
| CN108539154A (en) * | 2018-03-29 | 2018-09-14 | 龙岩学院 | A kind of porous carbon, carbon-selenium composite material and the method for preparing anode with carbon-selenium composite material |
| CN108777292A (en) * | 2018-05-23 | 2018-11-09 | 三峡大学 | A kind of anthracite is modified selenium/citric acid composite positive pole and preparation method thereof |
| CN109742354A (en) * | 2018-12-29 | 2019-05-10 | 贵州梅岭电源有限公司 | A kind of fluorination carbon composite electrode and preparation method thereof |
| CN109817920A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of preparation method and application of selenium enveloped carbon nanometer tube/graphene |
| CN110668509A (en) * | 2019-09-30 | 2020-01-10 | 南昌大学 | Selenium-coated high-nickel ternary layered positive electrode material and preparation method thereof |
| CN111342115A (en) * | 2020-02-29 | 2020-06-26 | 同济大学 | Electrolyte, lithium-selenium battery containing electrolyte and preparation method of lithium-selenium battery |
| CN111924881A (en) * | 2020-07-30 | 2020-11-13 | 内蒙古凯金新能源科技有限公司 | Molybdenum disulfide battery negative electrode material and preparation method thereof |
| CN112886016A (en) * | 2021-02-04 | 2021-06-01 | 陕西科技大学 | Preparation method of internal high-defect carbon nanotube composite material with through cobalt-nickel catalytic tube inner structure |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789623A (en) * | 2016-04-17 | 2016-07-20 | 中国计量大学 | Preparation device for selenium/carbon composite electrode material and control method |
| CN106935842B (en) * | 2017-03-08 | 2020-10-23 | 广东工业大学 | Plating solution for electroplating selenium, lithium-selenium battery positive electrode material and lithium-selenium battery |
| CN106935842A (en) * | 2017-03-08 | 2017-07-07 | 广东工业大学 | Electroplate plating solution, lithium selenium cell positive electrode and the lithium selenium cell of selenium |
| CN108539154A (en) * | 2018-03-29 | 2018-09-14 | 龙岩学院 | A kind of porous carbon, carbon-selenium composite material and the method for preparing anode with carbon-selenium composite material |
| CN108777292A (en) * | 2018-05-23 | 2018-11-09 | 三峡大学 | A kind of anthracite is modified selenium/citric acid composite positive pole and preparation method thereof |
| CN108777292B (en) * | 2018-05-23 | 2021-05-18 | 三峡大学 | Anthracite modified selenium/citric acid composite positive electrode material and preparation method thereof |
| CN109742354A (en) * | 2018-12-29 | 2019-05-10 | 贵州梅岭电源有限公司 | A kind of fluorination carbon composite electrode and preparation method thereof |
| CN109817920A (en) * | 2019-01-22 | 2019-05-28 | 陕西科技大学 | A kind of preparation method and application of selenium enveloped carbon nanometer tube/graphene |
| CN110668509A (en) * | 2019-09-30 | 2020-01-10 | 南昌大学 | Selenium-coated high-nickel ternary layered positive electrode material and preparation method thereof |
| CN111342115A (en) * | 2020-02-29 | 2020-06-26 | 同济大学 | Electrolyte, lithium-selenium battery containing electrolyte and preparation method of lithium-selenium battery |
| CN111924881A (en) * | 2020-07-30 | 2020-11-13 | 内蒙古凯金新能源科技有限公司 | Molybdenum disulfide battery negative electrode material and preparation method thereof |
| CN111924881B (en) * | 2020-07-30 | 2022-12-06 | 内蒙古凯金新能源科技有限公司 | Molybdenum disulfide battery cathode material and preparation method thereof |
| CN112886016A (en) * | 2021-02-04 | 2021-06-01 | 陕西科技大学 | Preparation method of internal high-defect carbon nanotube composite material with through cobalt-nickel catalytic tube inner structure |
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