CN109346646B - Novel lithium-sulfur battery diaphragm material, preparation method and application - Google Patents
Novel lithium-sulfur battery diaphragm material, preparation method and application Download PDFInfo
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- CN109346646B CN109346646B CN201811154611.6A CN201811154611A CN109346646B CN 109346646 B CN109346646 B CN 109346646B CN 201811154611 A CN201811154611 A CN 201811154611A CN 109346646 B CN109346646 B CN 109346646B
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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 belongs to the technical field of lithium-sulfur battery diaphragm materials, relates to a preparation method of a lithium-sulfur battery interlayer material, and more particularly relates to a preparation method of a bimetallic oxide doped graphene lithium-sulfur battery interlayer material, and specifically relates to a novel lithium-sulfur battery diaphragm material, a preparation method and an application. The invention relates to a method for preparing NiMoO by a one-step hydrothermal method4And preparing a functional separator material by combining spray drying to control the shuttle effect of lithium polysulfide in the lithium-sulfur battery. The bimetallic oxide doped graphene material with small particle size and uniform distribution is prepared by using a simple test method and process steps, and the prepared rGO/NiMoO is prepared by adopting spray drying4The material is innovative, rGO/NiMoO4The membrane has excellent electrochemical performance when used as a lithium sulfur battery interlayer.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery diaphragm materials, relates to a preparation method of a lithium-sulfur battery interlayer material, and more particularly relates to a preparation method of a bimetallic oxide doped graphene lithium-sulfur battery interlayer material, and specifically relates to a novel lithium-sulfur battery diaphragm material, a preparation method and an application.
Background
With the rapid development of the fields of mobile terminals, electric vehicles, new energy development and the like, the lithium ion battery system widely applied at present is increasingly difficult to meet various requirements, and in recent years, the research on the high-energy-density secondary battery based on the metal lithium has been paid unprecedented attention. The theoretical energy density of the lithium-sulfur battery is as high as 2600wh kg-1The advantages of rich resources, environmental friendliness and the like are widely concerned in the world, and are the main research direction of the next generation of lithium batteries.
The lithium-sulfur battery consists of a sulfur composite positive electrode, a metallic lithium negative electrode and an electrolyte therebetween. Because elemental sulfur is a poor conductor of electrons, the sulfur composite positive electrode generally consists of the elemental sulfur, a conductive agent and a polymer binder, and is different from a lithium removal-lithium insertion mechanism of a commercial lithium ion battery positive electrode. Elemental sulfur is first reduced to elemental sulfurPolysulfide S dissolved in electrolyten 2-(4. ltoreq. n.ltoreq.8), polysulfides are not single stable chemical components but mixtures of stable chemical components and unstable components including free radicals. As the discharge process proceeds, polysulfide is further reduced to sulfur ion S in lower valence state2-Or persulfate ions S2 2-Since the solubility of lithium sulfide and lithium sulfide in the organic electrolyte is low, the final discharge product precipitates on the conductive framework of the positive electrode in the form of solid lithium sulfide and lithium sulfide. The process of change of the sulfur-containing component of the active material during charge is the reverse of the above-described discharge process, which indicates that a large amount of the active material exists in the form of soluble polysulfide in the organic electrolyte during charge and discharge of the lithium-sulfur battery. The electrolyte containing polysulfide (also called liquid anode) can not only get and lose electrons at the anode to generate electrochemical reaction in the process of charging and discharging, but also can generate chemical reaction with the metallic lithium cathode with strong reducibility. The self-discharge process is shown in the discharge process, so that the utilization rate of the active material is low; in the charging process, high-valence polysulfide reacts with the metallic lithium cathode to generate low-valence polysulfide, and the low-valence polysulfide diffuses to the anode to be oxidized into high-valence polysulfide and then diffuses back to the cathode for continuous reaction. The whole process forms a closed cycle, and the external circuit shows a remarkable battery overcharge process, and the phenomenon is called shuttle effect.
The shuttle effect is serious, which not only causes the rapid attenuation of the battery capacity and the low utilization rate of the active material, but also causes the volume expansion effect in the charging and discharging process and the unstable electrochemical performance of the battery.
In the prior art, a scheme for improving the performance of a lithium-sulfur battery is to mechanically compound elemental sulfur and a porous material with a high pore structure by a filling, mixing or coating method to form a positive electrode composite material, design various main body materials for fixing sulfur, and develop a new electrolyte additive and other electrode protection strategies, so as to improve the lithium ion conductivity of a sulfur-based positive electrode and the cycle performance of the battery, however, the shuttling effect is still unavoidable. Moreover, during the manufacturing process, the harsh conditions of high cost and complex process are inevitable, which seriously hinders the commercialization of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to solve the problems in a lithium-sulfur battery, and provides a preparation method of a bimetallic oxide doped graphene lithium-sulfur battery interlayer material, in particular to a novel lithium-sulfur battery diaphragm material, a preparation method and application. The invention relates to a method for preparing NiMoO by a one-step hydrothermal method4And preparing a functional separator material by combining spray drying to control the shuttle effect of lithium polysulfide in the lithium-sulfur battery.
The technical scheme of the invention is as follows:
a preparation method of a novel lithium-sulfur battery diaphragm material comprises the following specific steps:
the first step is as follows: preparation of bimetallic oxide NiMoO4
Mixing 5-50mol/L nickel nitrate solution and 5-50mol/L sodium molybdate solution, magnetically stirring for 10-20 minutes, transferring the solution to a hydrothermal reaction kettle, sealing, preserving heat for 3-10 hours at 150 ℃ and 180 ℃ in an oven, collecting precipitate after natural cooling, washing with deionized water, and drying for 6-12 hours at 60-80 ℃ in the oven to obtain the NiMoO4。
The second step is that: preparation of NiMoO4@ rGO material
The NiMoO dried in the first step is dried4Mixing the powder and 2mg/ml graphene, carrying out ultrasonic treatment on the mixed solution for 1-2 hours, stirring for 10-20 hours, carrying out spray drying at the temperature of 200-220 ℃, collecting the powder obtained by spray drying, and preparing the NiMoO4@ rGO material.
The third step: preparation of NiMoO4@ rGO diaphragm material
The NiMoO prepared in the second step4Mixing the @ rGO material, conductive carbon black and PVDF in an NMP solution, grinding for 30-60 minutes, then coating on a clean diaphragm, and drying at 50-70 ℃ to obtain the NiMoO4@ rGO diaphragm material.
The invention is also characterized in that:
the stirring is magnetic stirring, and the rotating speed is 100-300 r/min.
Preferably, in the first step, the ratio of nickel nitrate: the molar ratio of sodium molybdate is 1: 1-1: 2.
preferably, in the second step, NiMoO4The molar ratio of powder to graphene is 2: 1-3:1.
Preferably, in the third step, NiMoO is added4Mixing the @ rGO material, the conductive carbon black and the PVDF in an NMP solution in a mass ratio of NiMoO4@ rGO material: conductive carbon black: PVDF =6:1:1-9:1: 1.
Preferably, in the third step, wherein the conductive carbon black: the mass ratio of PVDF was 1: 1.
The above NiMoO4The preparation method of the @ rGO lithium sulfur battery diaphragm material is characterized in that the related raw materials are all obtained by commercial purchase.
A novel lithium-sulfur battery diaphragm material prepared by the preparation method.
The novel lithium-sulfur battery diaphragm material obtained by the invention is applied to a lithium-sulfur battery as a lithium-sulfur diaphragm.
The invention has the beneficial effects that: the creativity of the invention lies in that the bimetallic oxide doped graphene material with smaller particle size and uniform distribution is prepared by using a simple test method and process steps, and the prepared rGO/NiMoO is prepared by adopting spray drying4The material is innovative, rGO/NiMoO4The membrane has excellent electrochemical performance when used as a lithium sulfur battery interlayer.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a scanning electron microscope photograph of the dual metal oxide spray-doped graphene material prepared in example 1.
FIG. 2 is a specific charge-discharge capacity curve of the NiMoO4@ rGO diaphragm battery prepared in example 1 at 0.2C cycle.
FIG. 3 shows NiMoO obtained in comparative experiment I4And (3) a discharge specific capacity cycle diagram of the separator material when the separator material is used as a battery separator.
Fig. 4 is a discharge specific capacity cycling plot of the rGO separator material obtained in comparative test two when used as a battery separator.
Detailed Description
The technical solutions of the present invention will be described more clearly and completely with reference to the following embodiments of the present invention. The described embodiments are merely exemplary embodiments of the invention, rather than limiting the invention in any way, and any variations, equivalents, modifications, etc. which fall within the spirit and scope of the invention are intended to be embraced therein.
The Graphene Oxide (GO) is synthesized from natural graphite by using a modified Hummers method, and the GO is dispersed in deionized water for 1 hour by ultrasonic treatment, wherein the concentration of the GO is 2 mg/ml.
Example 1
The first step is as follows: preparation of bimetallic oxide NiMoO4
Dissolving 2mmol of nickel nitrate in 30mL of deionized water, dissolving 2mmol of sodium molybdate in 30mL of deionized water, mixing the two solutions, magnetically stirring for 10 minutes, transferring the solution to a 100mL hydrothermal reaction kettle, sealing, keeping the temperature in an oven at 150 ℃ for 6 hours, naturally cooling, collecting precipitate, washing with deionized water, and drying in the oven at 60 ℃ for 12 hours to obtain the NiMoO4。
The second step is that: preparation of NiMoO4@rGO
The powder dried in the first step (1 g) was mixed with 200mL of graphene (2 mg/mL concentration). The above mixed solution was sonicated for 1 hour, and stirred for 10 hours and then spray-dried at 200 ℃. Collecting the spray-dried powder to obtain NiMoO4@ rGO material.
The third step: preparation of NiMoO4@ rGO diaphragm material
Mixing 0.7g of the NiMoO4@ rGO material prepared in the second step, 0.1g of conductive carbon black and 0.1g of pvdf in an NMP solution, grinding for 30 minutes, then coating on a clean diaphragm, and drying at 50 ℃ to obtain the NiMoO4@ rGO membrane material.
Pure sulfur is taken as a positive electrode material, metal lithium is taken as a counter electrode and a reference electrode, and a lithium sulfur electrolyte, NiMoO, is added4The @ rGO diaphragm material is a diaphragm, and a C is assembled in a glove box filled with argonR2025 button cell.
Fig. 1 is a scanning electron microscope photograph of the dual metal oxide spray-doped graphene material prepared in example 1. As is clear from FIG. 1, the bimetallic oxide is completely coated with graphene oxide, rGO/NiMoO4The shape of the material (NiMoO 4@ rGO diaphragm material) is a nano-scale microsphere, so that good conductivity can be provided for the transmission of ions in the lithium-sulfur battery, and meanwhile, the bimetallic ions can also cooperate to adsorb polysulfide together, so that a good inhibiting effect on the shuttle effect of polysulfide of the lithium-sulfur battery is achieved.
FIG. 2 is a NiMoO4The charge-discharge specific capacity curve of the @ rGO diaphragm battery in 0.2C circulation. As can be seen in FIG. 2, here rGO/NiMoO4When the material is used as a lithium-sulfur battery diaphragm material, the initial capacity is up to 1410mAg h-1Coulombic efficiency was also almost 100%. Readily known as NiMoO4The @ rGO interlayer plays a good role in inhibiting shuttling of polysulfide, and the electrochemical performance of the battery is improved.
Example 2
The first step is as follows: preparation of bimetallic oxide NiMoO4
Dissolving 3 mmol of nickel nitrate in 40mL of deionized water, dissolving 3 mmol of sodium molybdate in 35mL of deionized water, mixing the two solutions, magnetically stirring for 15 minutes, transferring the solution to a 100mL hydrothermal reaction kettle, sealing, keeping the temperature in an oven at 165 ℃ for 5 hours, naturally cooling, collecting precipitate, washing with deionized water, and drying in the oven at 70 ℃ for 8 hours to obtain the NiMoO4。
The second step is that: preparation of NiMoO4@ rGO material
The powder dried in the first step (1.5 g) was mixed with 350mL of graphene (2 mg/mL concentration). The above mixed solution was sonicated for 1.5 hours and stirred for 15 hours and then spray dried at 210 ℃. Collecting the spray-dried powder to obtain NiMoO4@ rGO material.
The third step: preparation of NiMoO4@ rGO diaphragm material
0.8g of NiMoO4@ rGO material and 0.1g of conductive carbon black and 0.1g of pvdf were mixed in NMP solution and ground for 40 minutesThen coating on a clean diaphragm, and drying at 60 ℃ to obtain the NiMoO4@ rGO membrane material.
Pure sulfur is taken as a positive electrode material, metal lithium is taken as a counter electrode and a reference electrode, and a lithium sulfur electrolyte, NiMoO, is added4The @ rGO diaphragm material is a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon gas.
Example 3
The first step is as follows: preparation of bimetallic oxide NiMoO4
Dissolving 4 mmol of nickel nitrate in 50mL of deionized water, dissolving 4 mmol of sodium molybdate in 40mL of deionized water, mixing the two solutions, magnetically stirring for 20 minutes, transferring the solution to a 100mL hydrothermal reaction kettle, sealing, keeping the temperature in an oven at 180 ℃ for 4 hours, naturally cooling, collecting precipitate, washing with deionized water, and drying in the oven at 80 ℃ for 6 hours to obtain the NiMoO4。
The second step is that: preparation of NiMoO4@ rGO material
The powder dried in the first step (2 g) was mixed with 500mL of graphene (2 mg/mL concentration). The above mixed solution was sonicated for 2 hours and stirred for 10 hours and then spray dried at 220 ℃. Collecting the spray-dried powder to obtain NiMoO4@ rGO material.
The third step: preparation of NiMoO4@ rGO diaphragm material
Mixing 0.9g of NiMoO4@ rGO material, 0.1g of conductive carbon black and 0.1g of pvdf in an NMP solution, grinding for 60 minutes, then coating on a clean diaphragm, and drying at 70 ℃ to obtain the NiMoO4@ rGO separator membrane.
Pure sulfur is taken as a positive electrode material, metal lithium is taken as a counter electrode and a reference electrode, and a lithium sulfur electrolyte, NiMoO, is added4The @ rGO diaphragm material is a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon gas.
In order to highlight the outstanding advantages of the material of the invention, the following two comparative experiments are provided.
Comparison test one: NiMoO4Separator and NiMoO4The @ rGO diaphragm was used for comparison.
Dissolving 2mmol of nickel nitrate in the solutionDissolving the mixture in 30mL of deionized water and 2mmol of sodium molybdate in 30mL of deionized water, mixing the two, magnetically stirring for 10 minutes, transferring the solution to a 100mL hydrothermal reaction kettle, sealing, keeping the temperature in an oven at 150 ℃ for 6 hours, naturally cooling, collecting precipitates, washing with deionized water, and drying in the oven at 60 ℃ for 12 hours to obtain the NiMoO4。
Mixing 0.7g of NiMoO4 material, 0.1g of conductive carbon black and 0.1g of pvdf in NMP solution, grinding for 30 minutes, coating on a clean diaphragm, and drying at 50 ℃ to obtain the NiMoO4A separator material.
Pure sulfur is taken as a positive electrode material, metal lithium is taken as a counter electrode and a reference electrode, and a lithium sulfur electrolyte, NiMoO, is added4The diaphragm material was a diaphragm, and the CR2025 button cell was assembled in a glove box filled with argon.
As can be seen in FIG. 3, NiMoO4The separator material was very ineffective in inhibiting shuttle in polysulfides, with a cell initial capacity of only 610mAh/g, much lower than NiMoO4The capacity of 1400mAh/g for the @ rGO membrane, which also illustrates pure NiMoO without the reduced graphene oxide providing high conductivity4The passage of the transmission of lithium ions may be blocked, resulting in a low capacity.
Comparative experiment two: rGO membranes and NiMoO4The @ rGO diaphragm was used for comparison.
500mL of graphene (2 mg/mL) solution was sonicated for 2 hours and stirred for 10 hours and then spray dried at 220 ℃. And collecting the powder obtained by spray drying to obtain the rGO material.
0.7g of the rGO material, 0.1g of conductive carbon black and 0.1g of pvdf are mixed in an NMP solution, ground for 30 minutes, coated on a clean diaphragm, and dried at 50 ℃ to obtain the rGO diaphragm material.
Pure sulfur is used as a positive electrode material, metal lithium is used as a counter electrode and a reference electrode, lithium sulfur electrolyte is added, a rGO diaphragm material is used as a diaphragm, and a CR2025 button cell is assembled in a glove box filled with argon.
As can be seen in fig. 4, the rGO separator material was very ineffective at inhibiting shuttling in polysulfides, with a cell initial capacity of only 580mAh/g which is far lower than NiMoO4The capacity of 1400mAh/g of the @ rGO membrane, which also indicates the absence of NiMoO4Under the condition of efficiently adsorbing polysulfide, the pure rGO is difficult to well adsorb excessive lithium, so that the utilization rate of active substances of a sulfur electrode is reduced, the lithium polysulfide can not be dissolved in electrolyte to be deposited on the surface of a lithium anode, and the performance of a lithium-sulfur battery is further reduced.
Claims (8)
1. A preparation method of a lithium-sulfur battery diaphragm material comprises the following specific steps:
the first step is as follows: preparation of the double Metal oxide NiMoO4
Mixing 5-50mol/L nickel nitrate solution and 5-50mol/L sodium molybdate solution, magnetically stirring for 10-20 minutes, transferring the solution to a hydrothermal reaction kettle, sealing, preserving heat for 3-10 hours at the temperature of 180 ℃ in an oven, collecting precipitates after natural cooling, washing with deionized water, and drying for 6-12 hours at the temperature of 60-80 ℃ in the oven to obtain NiMoO 4;
the second step is that: preparation of NiMoO4@ rGO Material
Mixing the NiMoO4 powder dried in the first step with 2mg/ml graphene, carrying out ultrasonic treatment on the mixed solution for 1-2 hours, stirring for 10-20 hours, carrying out spray drying at the temperature of 200-220 ℃, and collecting the powder obtained by spray drying to obtain a NiMoO4@ rGO material;
the third step: preparation of NiMoO4@ rGO diaphragm material
Mixing the NiMoO4@ rGO material prepared in the second step, conductive carbon black and PVDF in an NMP solution, grinding for 30-60 minutes, then coating on a clean diaphragm, and drying at 50-70 ℃ to obtain the NiMoO4@ rGO diaphragm material.
2. The preparation method of the lithium-sulfur battery separator material according to claim 1, wherein the stirring is magnetic stirring at a rotation speed of 100-300 r/min.
3. The method for preparing a separator material for a lithium-sulfur battery according to claim 1, wherein in the first step, the ratio of nickel nitrate: the molar ratio of sodium molybdate is 1: 1-1: 2.
4. the method for preparing the separator material for the lithium-sulfur battery according to claim 1, wherein in the second step, the molar ratio of the NiMoO4 powder to the graphene is 2: 1-3:1.
5. The method of preparing a lithium sulfur battery separator material of claim 1, wherein in the third step, the NiMoO4@ rGO material and conductive carbon black and PVDF are mixed in NMP solution at a mass ratio of NiMoO4@ rGO material: conductive carbon black: PVDF =6:1:1-9:1: 1.
6. The method for preparing a separator material for a lithium-sulfur battery according to claim 5, wherein, in the third step, the ratio of conductive carbon black: the mass ratio of PVDF was 1: 1.
7. A lithium sulfur battery separator material obtained by the method for preparing a lithium sulfur battery separator material according to any one of claims 1 to 6.
8. The use of the lithium sulfur battery separator material obtained by the method for preparing a lithium sulfur battery separator material according to any one of claims 1 to 6 as a lithium sulfur separator in a lithium sulfur battery.
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| CN107546357A (en) * | 2017-08-03 | 2018-01-05 | 清华大学 | Lithium-sulfur cell and its component, and application of the functional material layer in lithium-sulfur cell |
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| JP5568023B2 (en) * | 2011-01-12 | 2014-08-06 | 株式会社日立製作所 | Non-aqueous electrolyte battery |
| US20150162586A1 (en) * | 2013-12-05 | 2015-06-11 | Sion Power Corporation | New separator |
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| US20170117547A1 (en) * | 2015-06-05 | 2017-04-27 | Robert Bosch Gmbh | Cathode material for a lithium/sulfur cell |
| CN107546357A (en) * | 2017-08-03 | 2018-01-05 | 清华大学 | Lithium-sulfur cell and its component, and application of the functional material layer in lithium-sulfur cell |
| CN107978460A (en) * | 2017-11-21 | 2018-05-01 | 信阳师范学院 | A kind of preparation method of electrode material for super capacitor multilayer petal-shaped nickel molybdate |
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