CN108321438B - Full-graphite lithium-sulfur battery and preparation method thereof - Google Patents
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Abstract
The preparation method of the full-graphite lithium-sulfur battery comprises the steps of mixing porous graphite with elemental sulfur, loading sulfur into the porous graphite to prepare a graphite/sulfur composite material, mixing the graphite/sulfur composite material with a conductive agent and a binder, adding a solvent to prepare a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode piece; mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying to obtain a porous graphite negative electrode, and carrying out pre-lithiation treatment on the porous graphite negative electrode to obtain a lithium-embedded graphite negative electrode; and assembling the positive pole piece, the lithium-embedded graphite negative electrode and the diaphragm together, and adding electrolyte to prepare the lithium-sulfur battery. The invention uses porous graphite to prepare positive and negative electrodes, improves the electronic conductivity, relieves the shuttle effect of lithium polysulfide, and adopts the pre-lithiation porous graphite electrode to replace a metallic lithium negative electrode, thereby avoiding the generation of lithium dendrite and improving the safety of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur battery with an all-graphite structure.
Background
In recent years, portable electronic devices and electric vehicles have been developed rapidly, and thus, the demand for high specific energy and long cycle energy storage devices is more urgent. At present, the commercial lithium ion battery mainly adopts the intercalation reaction, the theoretical specific capacity is lower, and the energy density is difficult to break through 300 Wh/kg. Elemental sulfur has higher theoretical specific capacity (1675mAh/g), when the positive electrode adopts sulfur as an active substance and the negative electrode adopts metal lithium as an active substance, the theoretical energy density of the lithium-sulfur battery can reach 2600Wh/kg, the volume energy density reaches 3400Ah/L, and the cost of the elemental sulfur is lower, so the lithium-sulfur battery becomes a next-generation high-specific-energy battery with great potential.
However, the lithium-sulfur battery still has the following problems in practical application: firstly, elemental sulfur and a discharge end product are insulators, and the utilization rate of active substances is low; secondly, the intermediate product (lithium polysulfide) is dissolved in the electrolyte, so that the shuttle effect is caused, the capacity attenuation is fast, and the coulomb efficiency is low; third, lithium dendrite is easily generated in the lithium metal cathode, and the diaphragm is punctured, which causes a safety problem.
In order to solve the above problems, researchers have conducted a great deal of research to improve the electrochemical performance of lithium-sulfur batteries. For example, mesoporous carbon, conductive polymers and other materials are used as positive active material carriers to improve the electronic conductivity of the positive active material carriers. Or a polar substance material is used as a positive active substance carrier, and the dissolution of lithium polysulfide is reduced through the interaction between the carrier and the lithium polysulfide, so that the shuttle effect is relieved. Or lithium sulfide is used as a positive active material, and graphite, silicon and other materials are used for replacing lithium metal, so that potential safety hazards are eliminated. However, the above method still suffers from some technical limitations in the industrial preparation process of the battery, such as difficult coating of thick electrodes, easy occurrence of cracks during drying, and falling of active substances, and the complicated material preparation process is not suitable for mass production. And in the lithium-sulfur battery, the energy density which is comparable to that of a commercial lithium ion battery is required to be obtained, the sulfur content of the positive electrode composite material is required to be more than 75 wt%, and the sulfur loading capacity of the positive electrode plate is required to be 5mg/cm2The above. Therefore, there is still a need to further improve the electrochemical performance of lithium sulfur batteries.
Disclosure of Invention
The invention aims to provide an all-graphite lithium-sulfur battery and a preparation method thereof, which can solve the problems of poor cycle new energy, low coulombic efficiency and easy generation of lithium dendrite on a metal lithium cathode caused by non-conductivity of elemental sulfur and easy dissolution of lithium polysulfide in electrolyte.
In order to achieve the purpose, the invention adopts the following technical solutions:
the preparation method of the all-graphite lithium-sulfur battery comprises the following steps:
preparing a positive pole piece: mixing porous graphite and elemental sulfur in a mass ratio of 2-5: 5-8, loading sulfur into the porous graphite to prepare a graphite/sulfur composite material, mixing the graphite/sulfur composite material with a conductive agent and a binder, adding a solvent to prepare a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode piece;
preparing a negative pole piece: mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying to obtain a porous graphite negative electrode, and carrying out pre-lithiation treatment on the porous graphite negative electrode to obtain a lithium-embedded graphite negative electrode;
assembling the battery: and assembling the positive pole piece, the lithium-embedded graphite negative electrode and the diaphragm together, and adding electrolyte to prepare the lithium-sulfur battery.
The preparation method of the all-graphite lithium-sulfur battery comprises the following steps:
preparing a porous graphite electrode: mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain a porous graphite electrode;
preparing a negative pole piece: carrying out pre-lithiation treatment on the porous graphite electrode to obtain a lithium-intercalated graphite cathode;
assembling the battery: and assembling the porous graphite electrode, the lithium-embedded graphite cathode and the diaphragm together, firstly dropwise adding a solution containing long-chain lithium polysulfide onto the surface of the positive electrode current collector, and then adding an electrolyte to obtain the lithium-sulfur battery.
More specifically, the porous graphite is prepared by adopting the following method: ball-milling commercial graphite, thinning the particle size, dispersing the commercial graphite and a pore-forming agent into a solvent, and performing secondary granulation to obtain a precursor; and sintering the precursor at high temperature to realize hole expanding, removing the pore-forming agent, and drying to obtain the porous graphite.
More specifically, the porous graphite and the pore-forming agent are dispersed into a solvent according to the mass ratio of 1:4, and the solid content of the obtained solution is 10-30%.
More specifically, in the step of preparing the positive electrode plate, sulfur is loaded into porous graphite by adopting a melting diffusion method or an in-situ sulfur loading method to prepare the graphite/sulfur composite material.
More specifically, in the step of preparing the negative pole piece, the porous graphite negative pole is subjected to pre-lithiation by adopting a battery charging and discharging method or evaporation, hot pressing or dropwise adding a metal lithium powder solution on the surface of the pole piece to obtain the lithium-intercalated graphite negative pole.
More specifically, the solution containing long-chain lithium polysulfide contains 1M Li2S8Or Li2S6DOL/DME ═ 1:1 solution.
More specifically, the electrolyte is 1M LiTFSI and 0.1M LiNO3DOL/DME ═ 1:1 solution.
The full-graphite lithium-sulfur battery is prepared by adopting the preparation method.
According to the technical scheme, the porous graphite subjected to the hole expanding treatment is used as the carrier of the positive active material, and the porous graphite has good conductivity, so that the electronic conductivity of sulfur can be improved, the utilization rate of the active material is improved, and meanwhile, the porous graphite has a certain physical confinement effect on lithium polysulfide, so that the shuttle effect of the lithium polysulfide is relieved, the coulombic efficiency of a battery is improved, and the capacity attenuation is reduced. The porous graphite/sulfur composite material has higher compaction density, is easy to coat, is not easy to crack in the drying process, and can be used for preparing high-capacity electrodes; the pre-lithiated graphite cathode can form a stable SEI film on the surface of an electrode, prevent lithium polysulfide from reacting with metal lithium, generate a passivation layer on the surface, also play a role in relieving a shuttle effect and improving the coulombic efficiency of the lithium polysulfide, and can prevent potential safety hazards caused by the fact that a diaphragm is punctured due to the generation of lithium dendrites. The lithium-sulfur battery with the full graphite structure has the advantages of simple preparation process and low cost, and is suitable for batch production.
Drawings
FIG. 1 is a first charge-discharge curve diagram of a lithium-sulfur battery prepared in example 1 of the present invention at a rate of 0.5C;
FIG. 2 is a graph showing the cycle stability at 0.5C of a lithium sulfur battery prepared in example 2 of the present invention;
fig. 3 is a graph showing the cycle stability at 0.2C of the lithium sulfur battery prepared in example 3 of the present invention.
Detailed Description
In order to make the aforementioned and other objects, features and advantages of the invention more apparent, embodiments of the invention are described in detail below.
The basic idea of the invention is as follows: porous graphite is adopted as main base materials of the anode and the cathode, the porous graphite is obtained by expanding graphite, then, the porous graphite is subjected to pre-lithiation treatment to form a lithium-embedded stable graphite cathode, the porous graphite and a sulfur-containing material are compounded to form the anode, and finally, the graphite/sulfur anode and the lithium-embedded graphite cathode are assembled into the lithium-sulfur battery. The method comprises the following specific steps:
preparing porous graphite: ball milling graphite, thinning particle size, and mixing with pore-forming agent (KOH, NaCl, NH)4Cl, SiC and the like) are dispersed into a solvent (water or ethanol), and then secondary granulation is carried out to obtain a precursor; and sintering the precursor at a high temperature to realize hole expanding, then removing the pore-forming agent, and drying to obtain the porous graphite.
Preparing a graphite/sulfur composite anode: uniformly mixing porous graphite and elemental sulfur in a mass ratio of 2-5: 5-8, heating to 155 ℃, keeping for 12 hours, and cooling to obtain a graphite/sulfur composite material; mixing the graphite/sulfur composite material serving as a positive active substance with a conductive agent and a binder, adding a solvent to prepare uniform positive slurry, coating the positive slurry on the surface of an aluminum foil, and drying to obtain the positive pole piece.
Preparing a lithium-intercalated graphite negative electrode: mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare uniform negative electrode slurry, coating the negative electrode slurry on the surface of copper foil, drying, and then carrying out pre-lithiation treatment to obtain the negative electrode plate.
Assembling the battery: and assembling the positive pole piece, the negative pole piece and the diaphragm together, and adding electrolyte to prepare the lithium-sulfur battery.
The graphite/sulfur composite material can be prepared by using elemental sulfur as an active substance and adopting a melting diffusion method or an in-situ sulfur-carrying method. The lithium polysulfide can also be used as an active substance, the solution containing the lithium polysulfide is dripped on the surface of the porous graphite electrode, and the solution is directly used as the positive electrode of the lithium-sulfur battery after penetrating into the pore structure of the electrode and volatilizing.
The prelithiation of the graphite can be realized by charging and discharging the battery, or by means of evaporation, hot pressing and the like, or by dripping a metal lithium powder solution on the surface of the pole piece.
The present invention will be further illustrated by the following specific examples and comparative examples. The reagents, materials and instruments used in the following description are all conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents may be synthesized by a conventional synthesis method, if not specifically described.
Example 1
Preparing porous graphite: ball-milling commercial graphite at a ball-milling speed of 400rpm for 12 hours, dispersing the ball-milled graphite and KOH into an ethanol solvent in a mass ratio of 1:4 to obtain a solution with a solid content of 10-30%, and performing secondary granulation by adopting a closed spray drying method to obtain a precursor; and sintering the precursor at high temperature to realize hole expanding, finally removing the pore-forming agent by using 0.1M HCl solution, and drying at 80 ℃ for 12h to obtain the porous graphite.
Preparing a positive pole piece: mixing porous graphite and elemental sulfur in a mass ratio of 2:8, and loading sulfur into the porous graphite by adopting a melting diffusion method to obtain a graphite/sulfur composite material, wherein the sulfur content of the graphite/sulfur composite material is 75%; mixing the graphite/sulfur composite material with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP to form uniform slurry, then coating the uniform slurry on the surface of an aluminum foil, drying the uniform slurry for 12 hours at 50 ℃ to obtain a positive pole piece, wherein the sulfur loading capacity on the positive pole piece is 5mg/cm2The above.
Preparing a negative pole piece: mixing porous graphite with Super P and PVDF according to the mass ratio of 8:1:1, and adding NMP to form uniform slurryThen coating the copper foil surface with the porous graphite, and drying the copper foil surface at 120 ℃ for 12 hours to obtain a porous graphite cathode, wherein the porous graphite loading is 25mg/cm2The above; the porous graphite cathode is pre-lithiated through the charge and discharge of the battery, the porous graphite cathode and a lithium sheet are assembled into a half battery, and the electrolyte adopts 1MLiPF6EC of (1): DMC: and discharging the battery by using a polypropylene diaphragm as the diaphragm, so that lithium is embedded into the porous graphite negative electrode, finally detaching the lithium-embedded graphite pole piece, cleaning and drying to obtain the lithium-embedded graphite negative electrode.
Assembling the battery: and assembling the positive pole piece, the lithium-embedded graphite negative pole and the polypropylene diaphragm which are prepared in the previous steps together, and adding electrolyte to prepare the lithium-sulfur battery. The electrolyte adopts 1M LiTFSI and 0.1M LiNO3In a 1:1 (vol/vol) solution of DOL/DME in an amount of 15 μ L/mg.
The lithium-sulfur battery prepared in example 1 was subjected to a charge and discharge test, and fig. 1 is a graph showing the charge and discharge curves at 0.5C of the lithium-sulfur battery of this example. As can be seen from FIG. 1, the first discharge capacity of the lithium-sulfur battery prepared in this example reached 1149mAh/g, and the first charge capacity was 1127 mAh/g.
Example 2
This example differs from example 1 in that: when the porous graphite negative electrode is subjected to pre-lithiation, stable metal lithium powder is dispersed into an n-hexane solvent to form a uniform suspension, then the suspension is dropwise added to the surface of the porous graphite negative electrode, and after the n-hexane volatilizes, lithium and the porous graphite negative electrode are pressed to be embedded into the porous graphite negative electrode, so that the lithium-embedded graphite negative electrode is obtained. Wherein the amount of metallic lithium is controlled by the volume of the suspension.
Fig. 2 is a graph showing the cycle stability at 0.5C of the lithium-sulfur battery of this example. As can be seen from FIG. 2, the first discharge capacity of the lithium-sulfur battery prepared by the embodiment can reach 1140mAh/g, and the discharge capacity after 100 cycles is 905mAh/g, so that the lithium-sulfur battery has better stability.
Example 3
The porous graphite of this example was prepared by the same preparation method as in examples 1 and 2. After preparing the porous graphite, mixing the porous graphite with Super P and PVDF according to the mass ratio of 8:1:1, adding NMP to form uniform slurry, then coating the uniform slurry on the surface of copper foil, and drying at 120 ℃ for 12h to obtain the porous graphite electrode, wherein the porous graphite electrode can be used as a negative electrode of a battery after pre-lithiation treatment or can be directly used as a positive current collector, and the pre-lithiation treatment method of the embodiment is the same as that of embodiment 2.
Assembling the pre-lithiated lithium-intercalated graphite cathode with a porous graphite electrode and a polypropylene diaphragm together, and adopting lithium polysulfide (such as Li) containing 1M long chain2S8Or Li2S6) The solution of DOL/DME (volume ratio) 1:1 was used as a positive electrode active material, 30 μ L of the positive electrode active material solution was added dropwise to the surface of a positive electrode current collector (porous graphite electrode), and 30 μ L of an electrolyte solution was then supplemented, the electrolyte solution being 1M LiTFSI and 0.1M LiNO3The DOL/DME (1: 1) solution was assembled to obtain a lithium sulfur battery, and the electrolyte added was a conventional electrolyte.
The lithium sulfur battery prepared in example 3 was subjected to electrochemical performance test, in which the sulfur loading in the electrode sheet was 5.12mg/cm2. Fig. 3 shows the cycle performance curve of the lithium-sulfur battery of this example at 0.2C. As can be seen from FIG. 3, the first discharge capacity of the lithium-sulfur battery prepared by the embodiment can reach 1064mAh/g, and the discharge capacity after 80 cycles still has 1056mAh/g, so that the lithium-sulfur battery has better stability.
The lithium-sulfur battery of the invention uses porous graphite for preparing the positive electrode and the negative electrode, can improve the electronic conductivity, has a confinement effect on lithium polysulfide and relieves the shuttle effect of the lithium polysulfide, adopts the pre-lithiation porous graphite electrode to replace the metallic lithium negative electrode, is easy to form a stable SEI film, further relieves the shuttle effect, avoids the generation of lithium dendrite, improves the safety of the lithium-sulfur battery, and is easier to obtain the lithium-sulfur full battery with high specific energy compared with the prior art.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The preparation method of the all-graphite lithium-sulfur battery is characterized by comprising the following steps of:
preparing a positive pole piece: mixing porous graphite and elemental sulfur in a mass ratio of 2-5: 5-8, loading sulfur into the porous graphite to prepare a graphite/sulfur composite material, mixing the graphite/sulfur composite material with a conductive agent and a binder, adding a solvent to prepare a positive electrode slurry, coating the positive electrode slurry on a positive electrode current collector, and drying to obtain a positive electrode piece;
preparing a negative pole piece: mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying to obtain a porous graphite negative electrode, and carrying out pre-lithiation treatment on the porous graphite negative electrode to obtain a lithium-embedded graphite negative electrode;
assembling the battery: assembling the positive pole piece, the lithium-embedded graphite negative electrode and the diaphragm together, and adding electrolyte to prepare the lithium-sulfur battery;
the porous graphite is prepared by the following method: ball-milling commercial graphite, thinning the particle size, dispersing the commercial graphite and a pore-forming agent into a solvent, and performing secondary granulation to obtain a precursor; and sintering the precursor at high temperature to realize hole expanding, removing the pore-forming agent, and drying to obtain the porous graphite.
2. The preparation method of the all-graphite lithium-sulfur battery is characterized by comprising the following steps of:
preparing a porous graphite electrode: mixing porous graphite with a conductive agent and a binder, adding a solvent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain a porous graphite electrode;
preparing a negative pole piece: carrying out pre-lithiation treatment on the porous graphite electrode to obtain a lithium-intercalated graphite cathode;
assembling the battery: assembling a porous graphite electrode, a lithium-embedded graphite cathode and a diaphragm together, firstly dropwise adding a solution containing long-chain lithium polysulfide onto the surface of a positive electrode current collector, and then adding an electrolyte to obtain a lithium-sulfur battery;
the porous graphite is prepared by the following method: ball-milling commercial graphite, thinning the particle size, dispersing the commercial graphite and a pore-forming agent into a solvent, and performing secondary granulation to obtain a precursor; and sintering the precursor at high temperature to realize hole expanding, removing the pore-forming agent, and drying to obtain the porous graphite.
3. The method of manufacturing an all-graphite lithium-sulfur battery according to claim 1 or 2, characterized in that: dispersing porous graphite and a pore-forming agent into a solvent according to a mass ratio of 1:4, wherein the solid content of the obtained solution is 10-30%.
4. The method of manufacturing an all-graphite lithium-sulfur battery of claim 1, wherein: in the step of preparing the positive pole piece, sulfur is loaded into the porous graphite by adopting a melting diffusion method or an in-situ sulfur loading method to prepare the graphite/sulfur composite material.
5. The method of manufacturing an all-graphite lithium-sulfur battery according to claim 1 or 2, characterized in that: in the step of preparing the negative pole piece, the porous graphite negative pole is subjected to pre-lithiation by adopting a battery charging and discharging method or evaporation and hot pressing or by dropwise adding a metal lithium powder solution on the surface of the pole piece to obtain the lithium-embedded graphite negative pole.
6. The method of manufacturing an all-graphite lithium-sulfur battery of claim 2, wherein: the solution containing long-chain lithium polysulfide contains 1M Li2S8Or Li2S6DOL/DME ═ 1:1 solution.
7. The method of manufacturing an all-graphite lithium-sulfur battery according to claim 2 or 6, wherein: the electrolyte is 1MLiTFSI and 0.1M LiNO3DOL/DME ═ 1:1 solution.
8. Full graphite lithium sulphur battery, its characterized in that: prepared by the preparation method of any one of claims 1 to 7.
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| CN109950464A (en) * | 2019-02-01 | 2019-06-28 | 湖北锂诺新能源科技有限公司 | A kind of porous silicon-carbon cathode pole piece and preparation method thereof |
| CN111653728B (en) * | 2019-03-04 | 2022-02-01 | 中南大学 | Lithium-sulfur battery porous positive electrode and preparation method and application thereof |
| CN109778135A (en) * | 2019-03-28 | 2019-05-21 | 中国科学院青岛生物能源与过程研究所 | A kind of pre- insertion lithium metal prepares the device and method of cell negative electrode material |
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