CN109786669B - Lithium-sulfur battery and preparation method thereof - Google Patents
Lithium-sulfur battery and preparation method thereof Download PDFInfo
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- CN109786669B CN109786669B CN201910008922.XA CN201910008922A CN109786669B CN 109786669 B CN109786669 B CN 109786669B CN 201910008922 A CN201910008922 A CN 201910008922A CN 109786669 B CN109786669 B CN 109786669B
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The present invention provides a lithium-sulfur battery and a method for preparing the same, wherein the lithium-sulfur battery comprises: the lithium ion battery comprises a 3D lithium metal negative electrode, a sulfide positive electrode and an electrolyte membrane, wherein the electrolyte membrane is arranged between the 3D lithium metal negative electrode and the sulfide positive electrode. Wherein the 3D lithium metal negative electrode includes: the lithium ion battery comprises a 3D framework material, a lithium-philic layer, metal lithium and a solid electrolyte, wherein the lithium-philic layer covers the surface of a gap of the 3D framework material; the metal lithium is filled in the gaps of the 3D framework material; the solid electrolyte is filled in the gap of the 3D skeleton material. The lithium-sulfur battery and the preparation method thereof can effectively inhibit the generation of lithium dendrites, reduce the problems of volume expansion and the like, and improve the safety of a lithium-sulfur battery system.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to a lithium-sulfur battery and a preparation method thereof.
Background
With the rapid development of electric automobiles and mobile electronic devices, the demand of the current society for high-energy density lithium batteries is becoming increasingly prominent. Lithium sulfur battery having lithium metal as negative electrode and polysulfide as positive electrode, and method for producing the sameThe electrochemical reaction is as follows: 2Li + nS → Li2Sn(1≤n≤8)→Li2S is regarded as a lithium battery technology with a very promising prospect because the lithium battery has higher theoretical specific capacity and specific energy which can reach 1672mAh/g and 2600Wh/kg respectively, and the raw material resources are rich, the price is low, and the lithium battery is environment-friendly. Among them, lithium metal, as an ideal negative electrode material, has a higher theoretical specific capacity (3860mAh/g) and a lower potential (-3.04vs. standard hydrogen electrode) than graphite negative electrodes, and attracts people's attention. The lithium metal is adopted as the cathode material, so that the energy density of the battery can be effectively improved, the working voltage of the battery can be enlarged, and the energy attenuation of the battery can be reduced; however, there are significant drawbacks in conventional lithium sulfur battery designs: (1) the lithium metal is adopted as a negative electrode, and lithium ions can be deposited on the lithium metal to form dendrites in the charging process, so that the battery is easy to pierce through a diaphragm to cause short circuit and risk; (2) the electrolyte used in the traditional lithium-sulfur battery is liquid electrolyte, and the electrolyte of the lithium-sulfur battery with high specific energy is easily decomposed under large working current density, so that the multiplying power and the cycle performance are influenced; the phenomenon that polysulfide is dissolved in electrolyte and shuttled is serious, so that active substances are lost, the lithium metal negative electrode is damaged, and the battery capacity and the Kunlun efficiency are reduced; the generation of lithium dendrites can also increase the side reaction of the electrolyte and lithium metal, consume lithium active substances and reduce the utilization rate, and the electrolyte has the problems of flammability and easy explosion, so that the lithium-sulfur battery of the system has great potential safety hazard; (3) the lithium metal used as the negative electrode material also has a serious problem of electrode expansion in the circulation process, and can generate infinite relative volume change, thereby reducing the circulation coulomb efficiency and the service life of the battery. Therefore, it is important to design a safer lithium-sulfur battery system that can effectively inhibit the generation of polysulfide shuttle and lithium dendrite and reduce the volume expansion.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a lithium-sulfur battery and a method for manufacturing the same, which can effectively suppress the generation of lithium dendrites, reduce the volume expansion, and the like, and improve the safety of a lithium-sulfur battery system.
According to an aspect of the present invention, there is provided a lithium sulfur battery including, according to an embodiment of the present invention:
a 3D lithium metal negative electrode, the 3D lithium metal negative electrode comprising:
a 3D scaffold material;
a lithium-philic layer covering a surface of the void of the 3D scaffold material;
metallic lithium filled in voids of the 3D skeleton material;
a solid electrolyte filled in voids of the 3D skeletal material,
a sulfide positive electrode;
an electrolyte membrane disposed between the 3D lithium metal anode and the sulfide cathode.
The inventor of the invention finds that lithium dendrites are easy to generate in the negative electrode of lithium metal in the charging process and volume expansion can occur to cause short circuit of a battery, so that the 3D lithium metal negative electrode with a special three-dimensional structure is designed, a 3D framework material with the three-dimensional structure is used as a support structure with multiple gaps, a lithium-philic layer is uniformly coated on the surface of the 3D framework material to endow the surface of the support structure with lithium-philic performance, the nucleation overpotential of metal lithium filled in the gaps can be reduced, and the metal lithium is effectively induced to be uniformly nucleated on the 3D framework material in the charging and discharging process, so that the problems of generation of the lithium dendrites and the volume expansion in the charging and discharging process are reduced. In addition, the solid electrolyte is filled in the 3D framework material, so that an ion channel can be provided for the metal lithium, and the stability of the lithium-sulfur battery is improved.
Further, the 3D framework material is carbon fiber paper, foam copper or foam nickel, and preferably the carbon fiber paper.
Further, the thickness of the carbon paper is 100-200 microns, and the porosity is 70-75%.
Further, the solid electrolyte is a polymer-based electrolyte, an inorganic solid electrolyte, or a composite solid electrolyte.
Further, the polymer-based electrolyte is a PEO electrolyte, a PAN electrolyte, a PMMA electrolyte, a PVDF electrolyte, or a PEG electrolyte.
Further, the inorganic solid electrolyte is LLZO, an electrolyte LLTO electrolyte, a LATO electrolyte, a LIPON electrolyte, a LPS electrolyte, or an LPSC electrolyte.
Further, the composite solid electrolyte is a PEO-LLZO electrolyte, a PVDF-LLTO electrolyte or a PEO-LPS electrolyte.
Further, the electrolyte membrane is formed of the solid electrolyte.
Further, the content of the metal lithium in the 3D lithium metal negative electrode is 15-20 w/w%.
Further, the content of the solid electrolyte in the 3D lithium metal negative electrode is 10-20 w/w%.
In another aspect of the invention, the invention provides a method of making the lithium sulfur battery of the previous embodiment, the method comprising, according to an embodiment of the invention:
(1) providing a 3D scaffold material;
(2) soaking the 3D framework material in a precursor solution, and sintering to obtain a lithium-philic treated 3D framework material;
(3) sequentially injecting metal lithium and a solid electrolyte into the gaps of the lithium-philic treated 3D framework material so as to obtain a 3D lithium metal negative electrode;
(4) mixing vulcanized polymer, conductive carbon black and polyvinylidene fluoride according to a preset proportion, and adding the mixture into N-methyl-2-pyrrolidone so as to obtain anode slurry;
(5) coating the positive electrode slurry on an aluminum foil current collector, and performing vacuum drying to obtain a sulfide positive electrode;
(6) assembling the 3D lithium metal negative electrode, sulfide positive electrode, and electrolyte membrane to obtain the lithium sulfur battery.
Therefore, the lithium-sulfur battery prepared by the method adopts the 3D framework material with the three-dimensional structure as the support structure with multiple gaps, the surface of the support structure can be endowed with lithium affinity by uniformly coating the lithium affinity layer on the surface of the 3D framework material, the nucleation overpotential of the metal lithium filled in the gaps can be reduced, the metal lithium is effectively induced to be uniformly nucleated on the 3D framework material in the charging and discharging process, and the problems of lithium dendritic crystal generation and volume expansion in the charging and discharging process are reduced. In addition, the solid electrolyte is filled in the 3D framework material, so that an ion channel can be provided for the metal lithium, and the stability of the lithium-sulfur battery is improved.
Further, the precursor solution is a zinc-containing organic solution and comprises a zinc source, a surfactant and an organic solvent; wherein the zinc source comprises zinc acetate dihydrate, the surfactant comprises ethanolamine, and the organic solvent comprises n-propanol.
Further, the sintering process includes: drying at the temperature of 100-120 ℃ for 5-30 minutes, and then heating to 510-550 ℃ for sintering treatment for 10-30 minutes.
Further, in the step (3), metallic lithium is injected into the gaps of the lithium-philic treated 3D framework material, according to one of the following steps:
heating the metal lithium to 250-400 ℃ to melt the metal lithium into liquid lithium, and contacting the 3D framework material with the liquid metal lithium so as to enable the liquid lithium to be automatically immersed into the gaps of the 3D framework material.
Further, in the step (3), a solid electrolyte is injected into the voids of the lithium-philic treated 3D framework material, according to one of the following steps:
injecting the solid electrolyte into the gaps of the 3D framework material by adopting a melting method;
coating solid electrolyte slurry in the gaps of the 3D framework material by adopting a blade coating method;
and soaking the 3D framework material in the solid electrolyte slurry by adopting an immersion method so as to enable the solid electrolyte to be soaked in the gaps of the 3D framework material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a schematic structural view of a lithium sulfur battery according to an embodiment of the present invention;
fig. 2 is a schematic structural view of a 3D lithium metal negative electrode of a lithium sulfur battery according to an embodiment of the present invention;
fig. 3 is a flowchart of a method of manufacturing a lithium sulfur battery according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to one aspect of the invention, a lithium sulfur battery is provided.
According to an embodiment of the present invention, referring to fig. 1 to 2, a lithium sulfur battery 100 includes: a 3D lithium metal negative electrode 10, a sulfide positive electrode 20, and an electrolyte membrane 30. As shown in fig. 2, the 3D lithium metal negative electrode 10 includes: a 3D skeleton material 11, a lithium-philic layer 12, lithium metal 13, and a solid electrolyte 14, wherein the lithium-philic layer 12 covers a surface of a void of the 3D skeleton material 11; the metal lithium 13 is filled in the gap of the 3D framework material 11; the solid electrolyte 14 is filled in the void of the 3D skeleton material 11, and the electrolyte membrane 30 is disposed between the 3D lithium metal negative electrode 10 and the sulfide positive electrode 20. The sulfide positive electrode 20 includes a positive electrode tab current collector 21 and a mixture coating 22 of a positive active material, a conductive additive, and a binder formed on the positive electrode tab current collector 21.
The inventor of the invention finds that lithium dendrites are easy to generate in the negative electrode of lithium metal in the charging process and volume expansion can occur to cause short circuit of a battery, so that a 3D lithium metal negative electrode 10 with a special three-dimensional structure is designed, a 3D framework material 11 with the three-dimensional structure is used as a support structure with multiple gaps, a lithium-philic layer 12 is uniformly coated on the surface of the 3D framework material 11 to endow the support structure with surface lithium-philic performance, the nucleation overpotential of metal lithium 13 filled in the gaps can be reduced, and the metal lithium 13 is effectively induced to be uniformly nucleated on the 3D framework material 11 in the charging and discharging processes, so that the problems of generation of the lithium dendrites and the volume expansion in the charging and discharging processes are reduced. In addition, the solid electrolyte 14 is filled in the 3D framework material 11, so that an ion channel can be provided for the lithium metal, and the stability of the lithium-sulfur battery can be improved.
According to some embodiments of the present invention, the 3D skeleton material may be carbon fiber paper, copper foam or nickel foam. According to a specific embodiment of the present invention, the 3D skeleton material is preferably carbon fiber paper. It should be noted that, as shown in fig. 2, the carbon fiber paper herein specifically refers to a carbon fiber cloth woven by carbon fibers 112 with a diameter of 5 to 8 microns, and there is no binder between the carbon fibers 112; in fig. 2, only a few carbon fibers 112 are shown as an illustration, and the carbon fibers 112 form voids 111 therebetween, and the lithium-philic layer 12, the metallic lithium 13, and the solid electrolyte 14 in which one void 111 is filled are not shown in order to show the shape of the void 111. Thereby providing a better three-dimensional framework structure for the lithium metal and the solid-state electrolyte.
According to the embodiment of the invention, the thickness of the carbon fiber paper can be 100-200 microns, and the porosity can be 70-75%, so that the carbon fiber paper adopting the specifications has a higher specific surface area, compared with other current collectors, the weight of the electrode plate can be more effectively reduced, the effective contact area with the metal lithium 13 can be increased, the uniform nucleation of the metal lithium 13 on the surface of the carbon fiber paper can be more effectively induced, and the generation of lithium dendrites in the charging and discharging process can be further reduced. If the thickness of the carbon fiber paper is less than 100 micrometers, the lithium ion intercalation and deintercalation capability of the lithium metal composite electrode is insufficient, and if the thickness of the carbon fiber paper is more than 200 micrometers, the gaps in the carbon fiber paper are not easily filled with the metal lithium 13 and remain holes, so that the conductivity uniformity of the lithium metal composite electrode is influenced; if the porosity is less than 70%, the content of the metal lithium 13 in the lithium metal composite electrode is too low to affect the lithium ion intercalation and deintercalation capability of the composite electrode, and if the porosity is more than 75%, the voids 111 inside the carbon fiber paper are too large to have the effect of reducing the problem of volume expansion of the metal lithium 13 during the charge and discharge processes.
According to an embodiment of the present invention, in order to increase the affinity between the carbon fiber paper and the lithium metal 13, the material forming the lithium-philic layer 12 may be selected from at least one of germanium (Ge), aluminum (Al), nickel (Ni), magnesium (Mg) and silver (Ag), or zinc oxide (ZnO), aluminum oxide (Al), or the like2O3) And germanium dioxide (GeO)2) Thus, the lithium-philic layer 12 using the above material category can obviously induce the uniform nucleation of the lithium metal 13 on the surface of the carbon fiber paper. In some embodiments of the present invention, the material for forming the lithium-philic layer 12 may be zinc oxide (ZnO), and the thickness of the lithium-philic layer 12 may be 1 to 10 nm, so that the formation of the lithium-philic layer 12 on the surface of the void 111 of the carbon fiber paper may more efficiently induce the uniform nucleation of the lithium metal 13 on the surface of the carbon fiber paper.
According to the embodiment of the invention, the content of the metal lithium 13 in the 3D lithium metal negative electrode 10 can be 15-20 w/w%, and thus, for the carbon fiber paper with the porosity of 70-75%, the metal lithium 13 with the content is filled in the gap 111 covered by the lithium-philic layer 120, so that the 3D lithium metal negative electrode 10 has good lithium ion intercalation and extraction capability and lithium ion utilization rate. If the content of the metallic lithium 13 is less than 15 w/w%, the specific capacity of the lithium 3D lithium metal negative electrode 10 is too small, and if the content of the metallic lithium 13 is more than 30 w/w%, the effect of reducing the problem of volume expansion of the metallic lithium 13 during charge and discharge cannot be obtained.
According to an embodiment of the present invention, the content of the solid electrolyte 14 in the 3D lithium metal negative electrode 10 is 10-20 w/w%. Thereby, an ion channel can be efficiently provided. If the content of the solid electrolyte 14 is too small, lithium ions cannot normally pass through the separator to reach the lithium metal negative electrode, and a complete lithium ion path cannot be formed, and the battery cannot normally operate.
According to an embodiment of the present invention, the solid electrolyte is a polymer-based electrolyte, an inorganic solid electrolyte, or a composite solid electrolyte. According to a specific embodiment of the invention, the polymer-based electrolyte is a PEO electrolyte, a PAN electrolyte, a PMMA electrolyte, a PVDF electrolyte or a PEG electrolyte; the inorganic solid electrolyte is LLZO, LLTO electrolyte, LATO electrolyte, LIPON electrolyte, LPS electrolyte or LPSC electrolyte; the composite solid electrolyte is PEO-LLZO electrolyte, PVDF-LLTO electrolyte or PEO-LPS electrolyte.
According to a specific embodiment of the present invention, the above solid electrolyte is preferably a PEO electrolyte. Specifically, the PEO electrolyte adopted in the invention is obtained by uniformly stirring 500 ten thousand PEO with the molecular weight of 400-K as a raw material, acetonitrile as a solvent, silicon dioxide as an additive and LITFSI as a lithium salt at 40-60 ℃ by a magnetic stirrer.
According to an embodiment of the present invention, the above electrolyte membrane may be formed of the above solid electrolyte.
According to an embodiment of the present invention, the above-described electrolyte membrane 30 is preferably a PEO electrolyte membrane formed of a PEO electrolyte. Specifically, the PEO electrolyte membrane adopted in the invention is obtained by using 500 ten thousand PEO with the molecular weight of 400-inch as a raw material, acetonitrile as a solvent, silicon dioxide as an additive and LITFSI as a lithium salt, uniformly stirring the materials at 40-60 ℃ by using a magnetic stirrer, and then coating and drying the materials.
In general, solid electrolyte 14 and electrolyte membrane 30 employ the same type of polymer, in accordance with an embodiment of the present invention. For example, when the solid electrolyte 14 is a PEO electrolyte, the electrolyte membrane 30 may be a PEO electrolyte membrane. Whereby the stability of the lithium-sulfur battery can be further improved.
In summary, according to the embodiments of the present invention, a carbon fiber paper with multiple voids is selected as a 3D framework material, and a lithium-philic layer is coated on the surface of the voids of the carbon fiber paper to impart a lithium-philic property to the surface of a support structure, so as to reduce the nucleation overpotential of metal lithium filled in the voids, effectively induce the metal lithium to nucleate uniformly on the carbon paper during charging and discharging, and further reduce the generation of lithium dendrites during charging and discharging. In addition, the solid electrolyte is also filled in the 3D framework material, and ion channels can be effectively provided.
In another aspect of the present invention, the present invention provides a method of preparing the above-described lithium sulfur battery.
According to an embodiment of the present invention, referring to fig. 3, the preparation method includes:
s100: a 3D scaffold material is provided.
In this step, the 3D skeleton material 10 having a three-dimensional structure is provided as a porous support structure of the 3D lithium metal negative electrode 10. According to some embodiments of the present invention, the 3D skeleton material may be carbon fiber paper, copper foam or nickel foam. According to a specific embodiment of the present invention, the 3D skeleton material is preferably carbon fiber paper. The manner of providing the 3D framework material 10 is not particularly limited and may be purchased directly, and those skilled in the art may select the manner of providing the 3D framework material according to the specific size of the lithium metal composite electrode, which is not described herein again.
S200: and soaking the 3D framework material in a precursor solution, and sintering to obtain the 3D framework material subjected to lithium-philic treatment.
In this step, for example, the carbon fiber paper obtained in step S100 may be soaked in an organic solution containing zinc to be sufficiently wetted, and then taken out to be subjected to a sintering treatment, thereby obtaining a carbon fiber paper in which the surface of the voids 111 is uniformly coated with the lithium-philic layer 12.
According to an embodiment of the present invention, the precursor solution may be a zinc-containing organic solution, and includes a zinc source, a surfactant and an organic solvent, such that the zinc source may cover the nano-scale thickness of the lithium-philic layer 12 on the surface of the gap 111 after the subsequent sintering process, the surfactant may make the surface of the lithium-philic layer 12 more uniform, and the organic solvent facilitates the penetration of the zinc source into the gap 111 of the carbon fiber paper 11. In some specific examples, the zinc source is zinc acetate dihydrate, the surfactant is ethanolamine, and the organic solvent is n-propanol, so that the carbon fiber paper 11 can be sufficiently soaked in the zinc-containing organic solution mixed by the above materials and sintered at a high temperature, so that the surface of the void 111 of the carbon fiber paper 11 has lithium-philic property.
According to the embodiment of the present invention, the carbon fiber paper 11 fully impregnated with the zinc-containing organic solution is subjected to a sintering process, which specifically includes the following steps: drying at 100-120 ℃ for 5-30 minutes, and then raising the temperature to 510-550 ℃ for sintering treatment for 10-30 minutes. Thus, under the conditions of the sintering treatment, the zinc source on the surface of the void 111 can be sufficiently oxidized into the lithium-philic layer 12 of zinc oxide (ZnO), and the pre-drying step can firstly volatilize the organic solvent such as n-propanol, so as to prevent the organic solvent remained in the high-temperature sintering process from forming pores on the lithium-philic layer 12. If the pre-drying temperature is lower than 100 ℃ or the drying time is less than 5 minutes, pores still exist in the sintered lithium-philic layer 12; if the pre-drying temperature is higher than 120 ℃ or the drying time is longer than 30 minutes, the thickness uniformity of the lithium-philic layer 12 formed after the sintering treatment is reduced.
S300: and sequentially injecting metal lithium and a solid electrolyte into the gaps of the lithium-philic treated 3D framework material so as to obtain the 3D lithium metal negative electrode.
According to an embodiment of the present invention, in this step, metallic lithium is implanted into the voids of the lithium-philic treated 3D scaffold material according to the following steps: heating the metal lithium to 250-400 ℃ to melt the metal lithium into liquid lithium, and contacting the 3D framework material with the liquid metal lithium so as to enable the liquid lithium to be automatically immersed into the gaps of the 3D framework material.
According to an embodiment of the present invention, in this step S300, a solid electrolyte is injected into the voids of the lithium-philic treated 3D scaffold material, according to one of the following steps: the solid electrolyte may be injected into the voids of the 3D skeleton material using a fusion process; the solid electrolyte slurry can also be coated in the gaps of the 3D framework material by adopting a blade coating method; the 3D framework material may also be immersed in a solid electrolyte slurry using an immersion method such that the solid electrolyte is immersed in the voids of the 3D framework material.
Wherein: the solid electrolyte may be injected into the voids of the 3D skeleton material using a melting method, and specifically, the solid electrolyte membrane may be coated on the 3D skeleton material and heated to melt the solid electrolyte membrane into a liquid and be immersed in the voids of the 3D skeleton material. Thereby, the solid electrolyte can be more uniformly immersed into the gaps of the 3D framework material, thereby providing uniform and effective ion channels.
S400: mixing vulcanized polymer, conductive carbon black and polyvinylidene fluoride according to a preset proportion, and adding the mixture into N-methyl-2-pyrrolidone so as to obtain positive electrode slurry.
S500: coating the positive electrode slurry on an aluminum foil current collector, and performing vacuum drying to obtain a sulfide positive electrode;
according to the embodiment of the invention, vulcanized polymer, conductive carbon black (SP) and polyvinylidene fluoride (PVDF) are uniformly mixed in N-methyl-2-pyrrolidone (NMP) according to the mass ratio of 8:1:1 so as to obtain slurry, the slurry is uniformly coated on an aluminum foil current collector, and vacuum drying is carried out at 50 ℃ for 24 hours so as to obtain the sulfide cathode material.
In the invention, vulcanized polymer is used as a positive electrode material, and is mixed with conductive carbon black and polyvinylidene fluoride according to the mass ratio
S600: assembling the 3D lithium metal negative electrode, sulfide positive electrode, and electrolyte membrane to obtain the lithium sulfur battery.
According to the specific embodiment of the present invention, an electrolyte membrane, for example, a PEO electrolyte membrane, is coated on a prepared 3D lithium metal cathode, and is hot-rolled at 40-60 ℃ to make uniform contact, thereby reducing the interface resistance. Thereby, the electrolyte membrane can be effectively combined with the 3D lithium metal negative electrode.
Examples
A lithium-sulfur battery is prepared, which comprises a negative plate, a positive plate and a solid electrolyte layer.
Preparation of 3D lithium metal negative electrode: the method comprises the steps of adopting carbon fiber paper (the thickness of the carbon fiber paper is about 100-200 mu m, the diameter of carbon fibers is 5-10 mu m, and no binder is arranged among the carbon fibers) as a 3D framework material, heating a certain amount of lithium sheets to 250-400 ℃, melting the lithium sheets into liquid lithium, and then contacting the carbon fiber paper with the liquid metal lithium to enable the liquid lithium to be automatically immersed into pores of the carbon fiber paper. The amount of lithium in the carbon fiber paper can be controlled by the amount of molten lithium flakes.
Immersing PEO electrolyte into a 3D lithium metal negative electrode: the PEO electrolyte membrane is covered on the carbon fiber paper and heated at 70-140 ℃, and the PEO electrolyte membrane is uniformly immersed into pores of the carbon fiber paper after being melted into liquid. The amount of PEO impregnated into the pores of the carbon fiber paper can be controlled by controlling the thickness of the PEO film to form a uniform and continuous ion channel.
Combination of electrolyte membrane with 3D structure lithium metal negative electrode: a piece of PEO electrolyte membrane serving as a diaphragm is covered on a 3D negative electrode material filled with PEO, and is subjected to hot rolling at 40-60 ℃ to ensure that the PEO electrolyte membrane is contacted uniformly and the interface resistance of the PEO electrolyte membrane is reduced. The PEO electrolyte membrane is prepared by uniformly stirring PEO with the molecular weight of 400-500 ten thousand serving as a raw material, acetonitrile serving as a solvent, silicon dioxide serving as an additive and LITFSI serving as a lithium salt at 40-60 ℃ by a magnetic stirrer.
A sulfide positive electrode: uniformly mixing a vulcanized polymer, conductive carbon black (SP) and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 in N-methyl-2-pyrrolidone (NMP), uniformly coating slurry on an aluminum foil current collector, and carrying out vacuum drying at 50 ℃ for 24 hours to obtain the sulfide positive electrode material.
The 3D lithium metal negative electrode, the sulfide positive electrode, and the electrolyte membrane prepared as above were assembled to obtain the lithium sulfur battery. The electrochemical performance of the lithium-sulfur battery is tested, and through the test, the capacity retention rate of the lithium-sulfur battery prepared by the method is 85% after the lithium-sulfur battery is cycled for 100 weeks.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A method of making a lithium sulfur battery, comprising:
(1) providing a 3D scaffold material;
(2) soaking the 3D framework material in a precursor solution, and sintering to obtain a lithium-philic treated 3D framework material;
(3) sequentially injecting metal lithium and a solid electrolyte into the gaps of the lithium-philic treated 3D framework material so as to obtain a 3D lithium metal negative electrode;
(4) mixing vulcanized polymer, conductive carbon black and polyvinylidene fluoride according to a preset proportion, and adding the mixture into N-methyl-2-pyrrolidone so as to obtain anode slurry;
(5) coating the positive electrode slurry on an aluminum foil current collector, and performing vacuum drying to obtain a sulfide positive electrode;
(6) assembling the 3D lithium metal negative electrode, the sulfide positive electrode, and an electrolyte membrane to obtain the lithium sulfur battery,
in the step (2), the 3D framework material is soaked in a zinc-containing organic solution, then taken out, dried for 5-30 minutes at 100-120 ℃, and then heated to 510-550 ℃ for sintering treatment for 10-30 minutes, so that the lithium-philic treated 3D framework material is obtained;
in the step (3), injecting metallic lithium into the gaps of the lithium-philic treated 3D framework material, and performing one of the following steps: heating the metal lithium to the temperature of 250-400 ℃ to melt the metal lithium into liquid lithium, contacting the 3D framework material with the liquid metal lithium to ensure that the liquid lithium is automatically immersed into the gaps of the 3D framework material,
injecting a solid electrolyte into the voids of the lithium-philic treated 3D scaffold material according to one of the following steps: injecting the solid electrolyte into the gaps of the 3D skeleton material by a melting method,
the lithium sulfur battery includes:
a 3D lithium metal negative electrode, the 3D lithium metal negative electrode comprising:
a 3D scaffold material;
a lithium-philic layer covering a surface of the void of the 3D scaffold material;
metallic lithium filled in voids of the 3D skeleton material;
a solid electrolyte filled in voids of the 3D skeletal material,
a sulfide positive electrode;
an electrolyte membrane disposed between the 3D lithium metal anode and the sulfide cathode,
wherein the metal lithium and the solid electrolyte are both injected into the gaps of the 3D framework material by a melting method, the 3D framework material is carbon fiber paper, the thickness of the carbon fiber paper is 100-200 microns, and the void ratio is 70-75%; the content of the metal lithium in the 3D lithium metal negative electrode is 15-20 w/w%, and the content of the solid electrolyte in the 3D lithium metal negative electrode is 10-20 w/w%.
2. The method of claim 1, wherein the solid electrolyte is a polymer-based electrolyte, an inorganic solid electrolyte, or a composite solid electrolyte,
the polymer-based electrolyte is a PEO electrolyte, a PAN electrolyte, a PMMA electrolyte, a PVDF electrolyte or a PEG electrolyte;
the inorganic solid electrolyte is LLZO, LLTO electrolyte, LATO electrolyte, LIPON electrolyte, LPS electrolyte or LPSC electrolyte;
the composite solid electrolyte is PEO-LLZO electrolyte, PVDF-LLTO electrolyte or PEO-LPS electrolyte.
3. The method of making a lithium sulfur cell of claim 1 wherein the electrolyte membrane is formed from the solid electrolyte.
4. The method of claim 1, wherein the precursor solution is a zinc-containing organic solution and includes a zinc source, a surfactant, and an organic solvent; wherein the zinc source comprises zinc acetate dihydrate, the surfactant comprises ethanolamine, and the organic solvent comprises n-propanol.
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| CN201910008922.XA CN109786669B (en) | 2019-01-04 | 2019-01-04 | Lithium-sulfur battery and preparation method thereof |
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| CN201910008922.XA CN109786669B (en) | 2019-01-04 | 2019-01-04 | Lithium-sulfur battery and preparation method thereof |
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| CN112713260B (en) * | 2019-10-25 | 2022-12-23 | 广州汽车集团股份有限公司 | Flexible lithium metal battery cathode, preparation method thereof and lithium metal battery |
| CN113594425B (en) * | 2020-04-30 | 2022-12-27 | 中能中科（天津）新能源科技有限公司 | Composite carbon skeleton material, lithium-carbon material, and preparation method and application thereof |
| CN112382764B (en) * | 2020-11-12 | 2022-03-01 | 武汉理工大学 | Lithium-philic copper-nickel double-metal-layer modified three-dimensional framework material and preparation method and application thereof |
| CN113036268A (en) * | 2021-03-09 | 2021-06-25 | 重庆大学 | Lithium metal structure battery with structure energy storage function |
| WO2022204978A1 (en) * | 2021-03-30 | 2022-10-06 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical apparatus and electronic apparatus |
| CN113594414B (en) * | 2021-07-29 | 2023-03-24 | 溧阳紫宸新材料科技有限公司 | Organic porous skeleton cathode, preparation method thereof and battery |
| CN114628685B (en) * | 2021-08-09 | 2023-10-03 | 万向一二三股份公司 | Super-lithium-philic high-stability metal lithium composite negative plate and battery |
| CN114171716A (en) * | 2021-10-21 | 2022-03-11 | 中国人民解放军国防科技大学 | Solid-state composite metal lithium cathode with high electron/ion transmission characteristics and preparation method and application thereof |
| CN114141984B (en) * | 2021-12-01 | 2023-08-11 | 远景动力技术(湖北)有限公司 | Lithium battery and negative plate thereof and preparation method of negative plate |
| CN114388739B (en) * | 2022-03-24 | 2022-05-17 | 成都工业学院 | Composite lithium metal cathode, preparation method and application |
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