CN113346040A - Flexible integrated lithium-sulfur battery positive electrode material and preparation method thereof - Google Patents
Flexible integrated lithium-sulfur battery positive electrode material and preparation method thereof Download PDFInfo
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- CN113346040A CN113346040A CN202110542766.2A CN202110542766A CN113346040A CN 113346040 A CN113346040 A CN 113346040A CN 202110542766 A CN202110542766 A CN 202110542766A CN 113346040 A CN113346040 A CN 113346040A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a flexible integrated lithium-sulfur battery positive electrode material and a preparation method thereof. The method comprises the steps of constructing an ordered oxide \ hydroxide one-dimensional nanowire array in situ on a flexible substrate through hydrothermal synthesis, then pyrolyzing an organic matter at a high temperature in an oxygen-free atmosphere to realize gas-phase chemical deposition of the heteroatom-doped carbon nanotube on the surface of the nanowire, and simultaneously converting the corresponding oxide \ hydroxide into the corresponding metal or the corresponding derivative thereof to obtain the metal or the derivative thereof/the heteroatom-doped carbon nanotube three-dimensional sulfur-fixing carrier. The integrated electrode has stronger interface stability, obviously reduces the contact internal resistance of the battery, and the sulfur carrying amount of the sulfur anode is 3-20mg cm–2The cycling stability of the lithium-sulfur battery is effectively improved, and the overall energy density of the battery is improved. The invention integrates electricityThe insulating property of sulfur in the lithium-sulfur battery and the shuttle effect of intermediate products can be effectively improved, and the lithium-sulfur battery can be widely applied to wearable lithium-sulfur batteries.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material synthesis, and particularly relates to a flexible integrated lithium-sulfur battery positive electrode material and a preparation method thereof.
Background
With the rapid development of electronic technology in recent years, energy supply has become the greatest resistance that restricts the development thereof. At present, the lithium ion battery still occupies the vast majority of the energy storage market, but the traditional lithium ion battery taking graphite as a negative electrode and lithium iron phosphate or ternary materials as a positive electrode has limited energy density (350Wh kg)–1) It is difficult to satisfy the large-scale and high-power electricity demand. Therefore, the development of new battery systems with high energy density and high power density has become an important point and focus of research.
Among the new battery systems, lithium metal batteries have attracted much research interest due to their ultra-high energy density. Wherein the theoretical energy density of the lithium-sulfur battery is respectively as high as 2600Wh kg–1And the sulfur content in the nature is rich and nontoxic, and the energy storage system is one of the most ideal energy storage systems of the new generation. Meanwhile, lithium sulfur batteries can meet the increasing demand of electronic devices such as electric vehicles for higher weight and volumetric energy density of battery systems and lower cost and fewer safety problems. The concept of lithium sulfur batteries was first proposed by Herbet et al in 1962, but the problems of large battery polarization, low sulfur utilization, and poor cycle stability have not been solved effectively, and have gradually faded the line of sight.
At present, the commercial application of lithium-sulfur batteries is seriously affected by a plurality of problems still existing in the batteries. The sulfur positive electrode is specifically represented by: (1) sulfur and end discharge product lithium sulfide (Li)2S) high insulation, which directly results in the failure of normal charge and discharge of a battery system; (2) polysulfide as an intermediate product of discharge is very easy to dissolve in organic electrolyte and shuttles back and forth on the two sides of the anode and the cathode, so that the active ingredients are not fully utilized, the coulombic efficiency is low, and the polysulfide can severely corrode a lithium metal cathode; (3) the density difference between sulfur and discharge products is large, which causes severe volume expansion and pulverization phenomena of the electrode in the charging and discharging process. At present, research on anode carrier materials focuses on the aspect of powder, and relates to a fussy electrode preparation process, and meanwhile, the sulfur loading is still at a lower level, so that the energy density of a lithium-sulfur battery is seriously influenced. Therefore, the temperature of the molten metal is controlled,is crucial to the rational design of the positive electrode support of lithium-sulfur batteries.
In the research process of the powder electrode material, a metal current collector is inevitably used, but the surface of the metal current collector is smooth, and the bonding strength with an active material is insufficient, so that the bonding strength between the active material and the current collector is low, and the active material and the current collector can be separated in the charging and discharging process, so that the internal resistance of the battery is continuously increased, and the cycle life is reduced.
Disclosure of Invention
The invention provides a flexible integrated lithium-sulfur battery positive electrode material and a preparation method thereof, aiming at the problems of poor conductivity, low active ingredient loading capacity, low specific capacity, poor cycling stability and the like of the conventional lithium-sulfur battery positive electrode material. The preparation method comprises the steps of constructing an ordered oxide/hydroxide one-dimensional nanowire array in situ on a flexible substrate through hydrothermal synthesis, then using the one-dimensional nanowire array as a precursor, carrying out high-temperature pyrolysis on an organic matter in an oxygen-free atmosphere to obtain reducing gas, realizing gas-phase chemical deposition of the heteroatom-doped carbon nanotube on the surface of the nanowire, simultaneously converting the corresponding oxide/hydroxide into corresponding metal or a derivative thereof, and finally obtaining the metal or the derivative thereof/the heteroatom-doped carbon nanotube three-dimensional sulfur-fixing carrier, namely the flexible integrated lithium-sulfur battery anode material.
The preparation method of the flexible integrated lithium-sulfur battery positive electrode material comprises the following steps:
1) preparing a mixed solution of 0.1-5mM of transition metal salt and 0.5-25mM of urea, carrying out ultrasonic dispersion, transferring the mixed solution into a polytetrafluoroethylene lining of a hydrothermal kettle, putting a flexible substrate into the hydrothermal kettle, and reacting for 1-12 hours at 90-120 ℃; taking out and drying after the reaction is finished;
2) placing the dried product in the step 1) in an atmosphere furnace, simultaneously adding an organic compound containing hetero atoms, and roasting at the temperature of 500-1200 ℃ for 0.5-12h in an oxygen-free atmosphere to obtain a metal or derivative thereof/carbon nano tube composite three-dimensional sulfur-fixing carrier;
3) dispersing sulfur powder into CS2The medium-ultrasonic dispersion is uniform, the adding amount of sulfur powder is 6-100mg/mL, then the sulfur powder is dripped on the three-dimensional sulfur-fixing carrier obtained in the step 2), and the sulfur-fixing carrier is driedReacting at 140 ℃ and 170 ℃ for 10-15h to obtain the flexible integrated lithium-sulfur battery cathode material.
The transition metal salt in the step 1) is nitrate or/and chloride.
The transition metal salt is Co (NO)3)2、Zn(NO3)2、Ni(NO3)2、Fe(NO3)3、Cu(NO3)2、V(NO3)4、CoCl2、NiCl2、FeCl2、FeCl3、CuCl2、TiCl4、VCl4、MoCl5、CoSO4、NiSO4、FeSO4、Fe2(SO4)3、CuSO4、H8MoN2O4One or more of them.
The flexible substrate is selected from foamed nickel, foamed aluminum, carbon cloth, carbon paper or foamed carbon.
The oxygen-free atmosphere is nitrogen, argon or hydrogen.
Step 1) in-situ constructing a one-dimensional nanowire array on a flexible substrate, wherein the one-dimensional nanowire is CoO or Co3O4、ZnO、NiO、CuO、FeO、Fe2O3、MnO2、MoO3、TiO2、V2O5、CoMn2O4、NiCo2O4、NiCo2O4、CoV2O4、NiFe2O4、CoFe2O4、NiMoO4、NiTiO3、NiV2O6、NiMn2O4One or more of them.
The organic compound containing hetero atoms is one or more of boron, oxygen, nitrogen, sulfur, phosphorus, oxygen and fluorine.
The integrated electrode designed by the invention does not need the use of a conductive agent and a binder, and simultaneously omits the complicated electrode preparation processes such as slurry coating and the like. The integrated electrode of the invention grows the active component on the surface of the substrate in situ, has stronger interface stability and obviously reduces the battery connectionThe internal resistance is touched. The heteroatom-doped carbon nanotube and the nanowire array jointly construct a three-dimensional conductive network, so that the problem of poor conductivity of active ingredients can be effectively solved. The three-dimensional network space provided by the integrated electrode can provide a larger sulfur loading space and an expansion space in the charging and discharging process, and the sulfur loading amount of the sulfur anode is 3-20mg cm–2And the performance of the assembled soft package battery is also far higher than that of the soft package battery on the market. Meanwhile, the nanowire array is reduced into corresponding metal or derivatives thereof in the high-temperature treatment process, and the metal or the derivatives thereof are used as catalytic active ingredients, so that the cycling stability of the lithium-sulfur battery is effectively improved, and the overall energy density of the battery is improved. The integrated electrode can also effectively improve the insulativity of sulfur in the lithium-sulfur battery and the shuttle effect of an intermediate product, and can be widely applied to novel high-performance wearable lithium-sulfur batteries.
Drawings
Fig. 1 is a schematic diagram of the present invention for preparing a positive electrode material of a flexible integrated lithium-sulfur battery.
FIG. 2 is a scanning electron microscope image of the in-situ grown one-dimensional cobalt hydroxide nanowire array in example 1. The prepared cobalt hydroxide precursor presents a nanowire array structure, and the length of the nanowire array structure is about 4 micrometers. The nanowire structure provides enough space for the subsequent growth of the carbon nanotube.
FIG. 3 is a scanning electron micrograph of the three-dimensional sulfur-fixing carrier prepared in example 1. After the carbon nano tube is generated on the cobalt hydroxide precursor through in-situ catalysis (the diameter of the carbon nano tube is about 50nm), the carbon nano tube presents a crossed three-dimensional conductive carbon network structure, the ion migration rate in the battery is greatly improved, and sufficient space is provided for subsequent sulfur loading and battery reaction.
FIG. 4 is a scanning electron micrograph of the three-dimensional sulfur-fixing support prepared in example 1 after being loaded with sulfur. After sulfur is loaded, the prepared integrated electrode with the multilevel structure can still keep the original array structure, and the sulfur is uniformly coated on the surface of the integrated electrode.
Fig. 5 is a bendable soft package lithium-sulfur battery assembled by the flexible integrated electrode material prepared in example 1. The prepared flexible electrode material is assembled into a soft package battery, so that stable charging and discharging behaviors can be realized under different bending conditions, and the flexible electrode material is beneficial to popularization and application in flexible energy storage devices.
Fig. 6 is an electrical performance test chart of a lithium-sulfur soft package battery assembled by the flexible integrated electrode material prepared in example 1. The prepared flexible electrode material is assembled into a soft package battery, stable circulation can be achieved for 200 times under the current density of 2C, and the coulombic efficiency is maintained to be more than 97%.
Detailed Description
[ example 1 ]
Preparing 100mL of 5mM cobalt nitrate and 25mM urea mixed solution, transferring the mixed solution into a reaction kettle after ultrasonic dispersion, placing a foamed nickel substrate into the reaction kettle, and then carrying out high-temperature reaction at 120 ℃ for 6 hours; obtaining foamed nickel of in-situ grown one-dimensional cobalt hydroxide nanowire array;
b, putting the prepared foamed nickel of the in-situ grown one-dimensional cobalt hydroxide nanowire array into an atmosphere furnace, adding 0.1g of ZIF-67 serving as a carbon source, and continuously roasting at 800 ℃ for 2 hours under the condition of introducing nitrogen to obtain a three-dimensional sulfur-fixing carrier;
and c, dispersing 50mg of sulfur powder in 1mL of carbon disulfide, performing ultrasonic dispersion, then dropwise adding the sulfur powder to the three-dimensional sulfur-fixing carrier obtained in the step b, drying the sulfur powder in a 60 ℃ drying oven, and then heating the sulfur powder in a 155 ℃ drying oven for 12 hours to finally obtain the flexible integrated lithium-sulfur battery anode.
[ example 2 ]
Preparing 100mL of 5mM nickel nitrate and 25mM urea mixed solution, transferring the mixed solution into a reaction kettle after ultrasonic dispersion, placing a foamed nickel substrate into the reaction kettle, and then carrying out high-temperature reaction at 120 ℃ for 6 hours; obtaining foamed nickel of in-situ grown one-dimensional nickel hydroxide nanowire array;
b, putting the prepared foamed nickel of the in-situ grown one-dimensional nickel hydroxide nanowire array into an atmosphere furnace, adding 0.1g of ZIF-67 serving as a carbon source, and continuously roasting at 800 ℃ for 2 hours under the condition of introducing nitrogen to obtain a three-dimensional sulfur-fixing carrier;
and c, dispersing 50mg of sulfur powder in 1mL of carbon disulfide, performing ultrasonic dispersion, then dropwise adding the sulfur powder to the three-dimensional sulfur-fixing carrier obtained in the step b, drying the sulfur powder in a 60 ℃ drying oven, and then heating the sulfur powder in a 155 ℃ drying oven for 12 hours to finally obtain the flexible integrated lithium-sulfur battery anode.
[ example 3 ]
Preparing 100mL of 5mM titanium nitrate and 25mM urea mixed solution, transferring the mixed solution into a reaction kettle after ultrasonic dispersion, placing a foamed nickel substrate into the reaction kettle, and then carrying out high-temperature reaction at 120 ℃ for 6 hours; obtaining foamed nickel of in-situ grown one-dimensional titanium hydroxide nanowire arrays;
b, putting the prepared foamed nickel of the in-situ grown one-dimensional titanium hydroxide nanowire array into an atmosphere furnace, adding 0.1g of ZIF-67 serving as a carbon source, and continuously roasting at 800 ℃ for 2 hours under the condition of introducing nitrogen to obtain a three-dimensional sulfur-fixing carrier;
and c, dispersing 50mg of sulfur powder in 1mL of carbon disulfide, performing ultrasonic dispersion, then dropwise adding the sulfur powder to the three-dimensional sulfur-fixing carrier obtained in the step b, drying the sulfur powder in a 60 ℃ drying oven, and then heating the sulfur powder in a 155 ℃ drying oven for 12 hours to finally obtain the flexible integrated lithium-sulfur battery anode.
[ example 4 ]
Preparing 100mL of 5mM ammonium molybdate and 25mM urea mixed solution, transferring the mixed solution into a reaction kettle after ultrasonic dispersion, placing a foamed nickel substrate into the reaction kettle, and then carrying out high-temperature reaction at 120 ℃ for 6 hours; obtaining foamed nickel of in-situ grown one-dimensional molybdenum oxide nanowire arrays;
b, putting the prepared foamed nickel of the in-situ grown one-dimensional molybdenum oxide nanowire array into an atmosphere furnace, adding 0.1g of ZIF-67 serving as a carbon source, and continuously roasting at 800 ℃ for 2 hours under the condition of introducing nitrogen to obtain a three-dimensional sulfur-fixing carrier;
and c, dispersing 50mg of sulfur powder in 1mL of carbon disulfide, performing ultrasonic dispersion, then dropwise adding the sulfur powder to the three-dimensional sulfur-fixing carrier obtained in the step b, drying the sulfur powder in a 60 ℃ drying oven, and then heating the sulfur powder in a 155 ℃ drying oven for 12 hours to finally obtain the flexible integrated lithium-sulfur battery anode.
Claims (7)
1. A preparation method of a flexible integrated lithium-sulfur battery positive electrode material is characterized by comprising the following specific steps:
1) preparing a mixed solution of 0.1-5mM of transition metal salt and 0.5-25mM of urea, carrying out ultrasonic dispersion, transferring the mixed solution into a polytetrafluoroethylene lining of a hydrothermal kettle, putting a flexible substrate into the hydrothermal kettle, and reacting for 1-12 hours at 90-120 ℃; taking out and drying after the reaction is finished;
2) placing the dried product in the step 1) in an atmosphere furnace, simultaneously adding an organic compound containing hetero atoms, and roasting at the temperature of 500-1200 ℃ for 0.5-12h in an oxygen-free atmosphere to obtain a metal or derivative thereof/carbon nano tube composite three-dimensional sulfur-fixing carrier;
3) dispersing sulfur powder into CS2Uniformly dispersing the mixture by medium-ultrasound, wherein the adding amount of sulfur powder is 6-100mg/mL, then dropwise adding the mixture onto the three-dimensional sulfur-fixing carrier obtained in the step 2), drying, and reacting at the temperature of 140-170 ℃ for 10-15h to obtain the flexible integrated lithium-sulfur battery cathode material.
2. The method according to claim 1, wherein the transition metal salt in step 1) is a nitrate or/and chloride.
3. The method according to claim 1, wherein the transition metal salt is Co (NO)3)2、Zn(NO3)2、Ni(NO3)2、Fe(NO3)3、Cu(NO3)2、V(NO3)4、CoCl2、NiCl2、FeCl2、FeCl3、CuCl2、TiCl4、VCl4、MoCl5、CoSO4、NiSO4、FeSO4、Fe2(SO4)3、CuSO4、H8MoN2O4One or more of them.
4. The method of claim 1, wherein the flexible substrate is selected from the group consisting of nickel foam, aluminum foam, carbon cloth, carbon paper, and carbon foam.
5. The method of claim 1, wherein the oxygen-free atmosphere is nitrogen, argon, or hydrogen.
6. The method as claimed in claim 1, wherein step 1) is carried out by in-situ constructing one-dimensional nanowire array on the flexible substrate, wherein the one-dimensional nanowires are CoO and Co3O4、ZnO、NiO、CuO、FeO、Fe2O3、MnO2、MoO3、TiO2、V2O5、CoMn2O4、NiCo2O4、NiCo2O4、CoV2O4、NiFe2O4、CoFe2O4、NiMoO4、NiTiO3、NiV2O6、NiMn2O4One or more of them.
7. The method according to claim 1, wherein the organic compound containing hetero atoms is an organic compound containing one or more of boron, oxygen, nitrogen, sulfur, phosphorus, oxygen, and fluorine.
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| CN114057241A (en) * | 2021-12-10 | 2022-02-18 | 福建工程学院 | Preparation method and application of self-supporting low-crystalline-phase nickel hydroxide nanosheet electrode inlaid with nickel molybdate nanoparticles |
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| CN114057241A (en) * | 2021-12-10 | 2022-02-18 | 福建工程学院 | Preparation method and application of self-supporting low-crystalline-phase nickel hydroxide nanosheet electrode inlaid with nickel molybdate nanoparticles |
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Application publication date: 20210903 |