CN108565386B - Lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery and preparation method thereof - Google Patents
Lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lithium-sulfur battery diaphragm and a preparation method thereof, a lithium-sulfur battery and a preparation method thereof, and relates to the technical field of diaphragms, wherein the lithium-sulfur battery diaphragm comprises a support film, a nitrogen-doped carbon adsorption-conductive coating is compounded on the support film, and the preparation method of the lithium-sulfur battery diaphragm comprises the following steps: the nitrogen-doped carbon adsorption-conductive coating is coated on a support film, and after drying, the lithium-sulfur battery diaphragm is obtained, so that the technical problems that the traditional diaphragm basically has no barrier effect on polysulfide ions and can not block polysulfide dissolution and shuttling phenomena are solved.
Description
Technical Field
The invention relates to the technical field of diaphragms, in particular to a lithium-sulfur battery diaphragm and a preparation method thereof, and a lithium-sulfur battery and a preparation method thereof.
Background
With the increasing energy crisis and environmental pollution, rechargeable batteries having excellent performance have become one of the important means for solving the above problems. The lithium ion battery has the advantages of long cycle life, high working voltage, less pollution and the like, so that the lithium ion battery is more and more widely applied. However, the application of lithium ion batteries in electric vehicles and large-scale energy storage devices is limited by the problems of low energy density of the batteries, high cost of the batteries, and safety of the batteries. It has become an urgent task to research high-performance batteries having high energy density, long cycle life, good safety, and low cost. To meet the social demand, the development of next-generation secondary batteries having high energy density and high safety is imminent.
Lithium sulfur batteries have attracted considerable social attention in recent years because of their higher energy density, lower manufacturing costs, and higher safety. The theoretical energy density of the lithium ion battery reaches 2600Wh/kg, which is far higher than that of the lithium ion battery commercialized at present. However, the reaction system of the lithium-sulfur battery is very complex, and the lithium polysulfide intermediate product is dissolved in the electrolyte during the charging and discharging process, which can cause the loss of the active material of the positive electrode, leading to the attenuation of the battery capacity, and simultaneously, the polysulfide can generate redox reaction with the metal lithium after reaching the negative electrode, forming the shuttle effect, and reducing the coulomb efficiency of the system. However, the current commercial polyethylene or polypropylene membrane has relatively high porosity and large micropore diameter in order to ensure high lithium ion conductivity, and the diameter of polysulfide ions is less than 1nm, so that the traditional membrane has basically no barrier effect on the polysulfide ions and cannot block polysulfide dissolution and shuttling phenomena.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the objectives of the present invention is to provide a lithium-sulfur battery separator for blocking polysulfide ions and reducing polysulfide dissolution and shuttling phenomena.
The lithium-sulfur battery diaphragm provided by the invention comprises a support film, wherein a nitrogen-doped carbon adsorption-conductive coating is compounded on the support film.
Further, the nitrogen-doped carbon adsorption-conductive coating is mainly prepared from nitrogen-doped porous carbon-carbon nanotube-graphene and an adhesive;
preferably, the mass ratio of the nitrogen-doped porous carbon-carbon nanotube-graphene to the binder is (80-99): (1-20).
Further, the nitrogen-doped porous carbon-carbon nanotube-graphene is mainly prepared from nano porous carbon, graphene and a carbon nanotube;
preferably, the mass ratio of the nanoporous carbon to the graphene to the carbon nanotube is (1-2): (2-3): (1-2).
Further, the nitrogen-doped porous carbon-carbon nanotube-graphene is mainly prepared from amino modified nano porous carbon, carboxylated graphene and carboxylated carbon nanotubes;
preferably, the preparation method of the nitrogen-doped porous carbon-carbon nanotube-graphene material comprises the following steps:
mixing the amino modified nano porous carbon, the carboxylated graphene and the carboxylated carbon nanotube, and carrying out condensation reaction to obtain nitrogen-doped porous carbon-carbon nanotube-graphene;
preferably, the condensation reaction is carried out under the action of an activator;
preferably, the activator is selected from at least one of N-hydroxysuccinimide, 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide, or N, N' -dicyclohexylcarbodiimide.
Further, the preparation method of the amino modified nanoporous carbon comprises the following steps:
(a) carboxylating the nano porous carbon to obtain carboxylated nano porous carbon;
(b) acylating and chlorinating the carboxylated nanoporous carbon to obtain an acylchlorinated nanoporous carbon;
(c) performing amino modification on the acyl chlorination nanoporous carbon to obtain amino modified nanoporous carbon;
preferably, in the step (a), firstly refluxing the nanoporous carbon and the mixed solution of sulfuric acid and nitric acid, then reacting the refluxed nanoporous carbon and the mixed solution of sulfuric acid and hydrogen peroxide, and refluxing to obtain the carboxylated nanoporous carbon;
preferably, in the step (b), the carboxylated nanoporous carbon and thionyl chloride are dissolved in an organic solvent for reaction, and then the acyl chloride nanoporous carbon is obtained through reflux;
preferably, in the step (c), the acyl chloride nanoporous carbon and ethylenediamine are dissolved in an organic solvent and react to obtain the amino modified nanoporous carbon.
Further, the nano porous carbon is selected from at least one of ketjen black, acetylene black, mesoporous carbon or carbon molecular sieve;
preferably, the carboxylated graphene is selected from a monolayer carboxylated graphene and/or a double multilayer carboxylated graphene;
preferably, the carboxylated carbon nanotubes are selected from single-walled carboxylated carbon nanotubes and/or multi-walled carboxylated carbon nanotubes.
Further, the support membrane is selected from at least one of a polyethylene porous membrane, a polypropylene porous membrane, a polyethylene/polypropylene composite membrane, a polyethylene porous membrane coated with an adhesive on two sides, a polypropylene porous membrane coated with an adhesive on two sides, a polyimide membrane or an aramid membrane;
preferably, the thickness of the support film is 16-25 μm;
preferably, the nitrogen-doped carbon adsorption-conductive coating has a thickness of 4 to 10 μm.
The invention also aims to provide a preparation method of the lithium-sulfur battery diaphragm, which comprises the following steps:
coating the nitrogen-doped carbon adsorption-conductive coating on a support film, and drying to obtain a lithium-sulfur battery diaphragm;
preferably, the nitrogen-doped porous carbon-carbon nanotube-graphene and the binder are dissolved in a solvent to prepare a slurry, the slurry is coated on a support membrane, and the support membrane is dried to obtain the lithium-sulfur battery separator.
The invention also aims to provide a lithium-sulfur battery, which comprises the lithium-sulfur battery diaphragm, a sulfur positive plate and a lithium negative plate;
preferably, the sulfur positive plate is mainly prepared by coating a positive electrode material on a positive electrode current collector;
preferably, the positive electrode material includes a positive electrode active material, a conductive agent, and a binder;
preferably, the positive electrode active material is a sulfur-carbon composite and/or sulfur;
preferably, the lithium negative electrode sheet is selected from at least one of a lithium electrode, a lithium carbon electrode, a lithium alloy electrode, or a modified coated lithium electrode.
The fourth object of the present invention is to provide a method for preparing the lithium-sulfur battery, comprising the steps of:
and placing the lithium-sulfur battery diaphragm between the sulfur positive plate and the lithium negative plate to assemble a coiled core, placing the coiled core into a lithium-sulfur battery shell, injecting electrolyte, and sealing to obtain the lithium-sulfur battery.
According to the lithium-sulfur battery diaphragm provided by the invention, the nitrogen-doped carbon adsorption-conductive coating is compounded on the support film, so that polysulfide can be adsorbed on the diaphragm to perform strong conductivity conversion, the shuttle effect of the polysulfide is inhibited, a current collector structure can be constructed on the interface of the positive electrode and the diaphragm, the interface reaction resistance is reduced, the polysulfide can be adsorbed, the sulfur-containing component can be activated, the dissolved sulfur on the interface of the positive electrode and the diaphragm can be effectively recovered, the utilization rate of active substances of the positive electrode is improved, the transmembrane diffusion of the polysulfide is limited, and the cycle performance of the lithium-sulfur battery is improved.
The preparation method of the lithium-sulfur battery diaphragm provided by the invention is simple in process, convenient to operate and suitable for industrial mass production.
According to the lithium-sulfur battery provided by the invention, the diaphragm of the traditional microporous film structure is replaced by the diaphragm of the lithium-sulfur battery provided by the invention, the utilization rate of the active substances of the positive electrode is improved, and the transmembrane diffusion of polysulfide is limited, so that the cycle performance of the lithium-sulfur battery is improved.
The preparation method of the lithium-sulfur battery provided by the invention is simple in process, convenient to operate and suitable for industrial mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a scanning electron microscope image of the nitrogen-doped porous carbon-carbon nanotube-graphene provided in embodiment 3 of the present invention;
fig. 2 is a charge-discharge curve of a lithium sulfur pouch battery provided in example 11 of the present invention and a lithium sulfur pouch battery provided in comparative example 8;
fig. 3 is a graph showing the cycle performance of the lithium sulfur pouch battery provided in example 3 of the present invention and the lithium sulfur pouch battery provided in comparative example 2.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the invention, the invention provides a lithium-sulfur battery diaphragm which comprises a support film, wherein a nitrogen-doped carbon adsorption-conductive coating is compounded on the support film.
According to the lithium-sulfur battery diaphragm provided by the invention, the nitrogen-doped carbon adsorption-conductive coating is compounded on the support film, so that polysulfide can be adsorbed on the diaphragm to perform strong conductivity conversion, the shuttle effect of the polysulfide is inhibited, a current collector structure can be constructed on the interface of the positive electrode and the diaphragm, the interface reaction resistance is reduced, the polysulfide can be adsorbed, the sulfur-containing component can be activated, the dissolved sulfur on the interface of the positive electrode and the diaphragm can be effectively recovered, the utilization rate of active substances of the positive electrode is improved, the transmembrane diffusion of the polysulfide is limited, and the cycle performance of the lithium-sulfur battery is improved.
In the invention, the nitrogen-doped carbon adsorption-conductive coating means a coating with adsorption and conductive functions of nitrogen-doped carbon.
In a preferred embodiment of the present invention, the nitrogen-doped carbon adsorption-conductive coating layer is mainly made of nitrogen-doped porous carbon-carbon nanotube-graphene and a binder.
The nitrogen-doped porous carbon-carbon nanotube-graphene and the adhesive are mixed and then coated on the support film to form the nitrogen-doped carbon adsorption-conductive coating.
In a preferred embodiment of the invention, the mass ratio of the nitrogen-doped porous carbon-carbon nanotube-graphene to the binder is (80-99): (1-20).
In typical but non-limiting embodiments of the invention, the mass ratio of nitrogen-doped porous carbon-carbon nanotube-graphene to binder is 80:20, 81:19|, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, 90:10, 91:19, 92:18, 93:17, 94:16, 95:15, 96:14, 97:13, 98:12, or 99: 1.
In a preferred embodiment of the present invention, the binder is selected from at least one of polyacrylic acid (PAA), Polytetrafluoroethylene (PTFE), polyvinylidene chloride (PVDF), Polyacrylamide (PAM), Styrene Butadiene Rubber (SBR), Hydroxypropylmethylcellulose (HPMC), Methylcellulose (MC), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives.
Acrylonitrile copolymers include, but are not limited to, LA132, LA133, and LA 135.
In a preferred embodiment of the present invention, the nitrogen-doped porous carbon-carbon nanotube-graphene material is mainly made of nanoporous carbon, graphene and carbon nanotubes.
The nano porous carbon has good adsorption performance, polysulfide can be effectively adsorbed, and graphene and carbon nano tubes have good conductivity.
The utility model discloses a carbon nanotube-graphite alkene, the utility model discloses a carbon nanotube-graphite alkene is connected with the strong electrically conductive phase (graphite alkene and carbon nanotube) of physical adsorption phase (nano porous carbon), the surface conduction of electron is realized to nano porous carbon, the nano porous carbon that graphite alkene and carbon nanotube made, with nano porous carbon load on graphite alkene, and utilize carbon nanotube to bridge between with nano porous carbon and link together, realize the line conduction of electron, make coexistence in same interface between physical adsorption phase (nano porous carbon), the chemical adsorption phase (containing nitrogen and oxygen functional group) and the strong electrically conductive phase (graphite alkene and carbon nanotube), polysulfide utilizes graphite alkene and carbon nanotube's strong conductivity.
In a preferred embodiment of the invention, the mass ratio of the nanoporous carbon, the graphene and the carbon nanotube is (1-2): (2-3): (1-2).
The nano porous carbon, the graphene and the carbon nano tube are cooperatively matched, so that the nano porous carbon-carbon nano tube-graphene has better conductivity and adsorption performance.
In a preferred embodiment of the present invention, the nanoporous carbon is an amine-modified nanoporous carbon, the graphene is carboxylated graphene, and the carbon nanotube is a carboxylated carbon nanotube.
The amino modified nano porous carbon, the carboxylated graphene and the carboxylated carbon nanotube are selected as raw materials, so that the amino modified nano porous carbon, the carboxylated graphene and the carboxylated carbon nanotube are subjected to condensation reaction, and the nano porous carbon-carbon nanotube-graphene is prepared.
In a preferred embodiment of the present invention, the method for preparing the nitrogen-doped porous carbon-carbon nanotube-graphene material comprises the following steps:
mixing the amino modified nano porous carbon, the carboxylated graphene and the carboxylated carbon nanotube, and carrying out condensation reaction to obtain the nitrogen-doped porous carbon-carbon nanotube-graphene.
In a further preferred embodiment of the present invention, after mixing the amino group modified nanoporous carbon, the carboxylated graphene and the carboxylated carbon nanotube, a condensation reaction activator is added to accelerate the condensation reaction process, so as to obtain the nitrogen-doped porous carbon-carbon nanotube-graphene.
In a preferred embodiment of the present invention,
in a further preferred embodiment of the invention, the amino group modified nanoporous carbon, the carboxylated graphene and the carboxylated carbon nanotube are placed in a reaction flask, N' -Dicyclohexylcarbodiimide (DCC) is added into a solvent at 90-100 ℃ for heating and refluxing for 48h, the reaction is followed by filtration, the excess DCC and other byproducts are washed away by absolute ethyl alcohol, and the nitrogen-doped porous carbon-carbon nanotube-graphene is obtained by vacuum drying at 60 ℃.
In a preferred embodiment of the invention, the preparation method of the amine-modified nanoporous carbon comprises the following steps:
(a) carboxylating the nano porous carbon to obtain carboxylated nano porous carbon;
(b) acylating and chlorinating the carboxylated nanoporous carbon to obtain an acylchlorinated nanoporous carbon;
(c) and performing amino modification on the acyl chlorination nanoporous carbon to obtain the amino modified nanoporous carbon.
In a preferred embodiment provided by the invention, the amino group modified nanoporous carbon is obtained by sequentially carboxylating and acylating-chlorinating the nanoporous carbon and then modifying the amino group.
In a further preferred embodiment of the present invention, in the step (a), the nanoporous carbon is refluxed with a mixed solution of sulfuric acid and nitric acid, and then the refluxed nanoporous carbon is reacted with a mixed solution of sulfuric acid and hydrogen peroxide, and the carboxylated nanoporous carbon is obtained by refluxing.
In a further preferred embodiment of the present invention, in the step (b), the carboxylated nanoporous carbon and thionyl chloride are dissolved in an organic solvent, reacted, and refluxed to obtain the acylchlorinated nanoporous carbon.
In a further preferred embodiment of the present invention, in the step (c), the amido-modified nanoporous carbon is obtained by dissolving the acylchlorinated nanoporous carbon and ethylenediamine in an organic solvent and reacting.
The invention provides a typical but non-limiting preparation method of aminated modified nanoporous carbon, which comprises the following steps:
(1) mixing nanoporous carbon with H2SO4With HNO3Mixed solution of (2) (98% H)2SO4:68％HNO33:1 (volume ratio)) according to the mass ratio of 1 (200-;
(2) placing the product of the step (1) in H2SO4And H2O2Mixed solution of (2) (98% H)2SO4:30％H2O24:1 (volume ratio)), refluxing at 70 ℃ for 0.5h, filtering, washing with deionized water until the pH of the filtrate is neutral, and vacuum drying the product in a vacuum oven for 24h to obtain carboxylNano porous carbon is formed;
(3) and (3) placing the product obtained in the step (2) into a reaction bottle, adding excessive thionyl chloride and an organic solvent, stirring and refluxing for 24 hours at 70 ℃, filtering, washing and drying to obtain the acyl-chlorinated nano porous carbon material.
(4) And (4) placing the product obtained in the step (3) into a reaction bottle, adding a certain amount of ethylenediamine, refluxing and stirring in an organic solvent at 75 ℃ for 48 hours, filtering, washing and drying to obtain the amino modified porous carbon.
And (3) placing the product obtained in the step (4) into a reaction bottle, adding a certain amount of carboxylated graphene, carboxylated carbon nanotubes and DCC, heating and refluxing for 48 hours in an organic solvent at 90-100 ℃, filtering after reaction, washing off redundant DCC and other byproducts by using absolute ethyl alcohol, and drying in vacuum at 60 ℃ to obtain the nitrogen-doped porous carbon-carbon nanotube-graphene.
In a preferred embodiment of the present invention, the organic solvent used in step (1) and step (2) is dimethylformamide.
In a preferred embodiment of the present invention, the organic solvent used in step (5) is benzene and/or toluene.
In a preferred embodiment of the present invention, the nanoporous carbon is selected from at least one of ketjen black, acetylene black, mesoporous carbon, or carbon molecular sieves.
In a preferred embodiment of the present invention, the carboxylated graphene is selected from a monolayer of carboxylated graphene and/or a multilayer of carboxylated graphene; the term "multilayered carboxylated graphene" refers to a carboxylated graphene having 2 or more layers.
In a preferred embodiment of the present invention, the carboxylated carbon nanotubes are selected from single-walled carboxylated carbon nanotubes and/or multi-walled carboxylated carbon nanotubes; wherein the multi-wall carboxylated carbon nanotube refers to a carboxylated carbon nanotube with more than 2 layers.
In a preferred embodiment of the present invention, the thickness of the support film is 16 to 25 μm, and the thickness of the nitrogen-doped carbon adsorption-conductive coating is 4 to 10 μm.
In typical but non-limiting embodiments of the invention, the support film has a thickness of 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 μm.
In typical but non-limiting embodiments of the present invention, the thickness of the nitrogen-doped carbon adsorption-conductive coating is 4, 5, 6, 7, 8, 9, or 10 μm.
In a preferred embodiment of the present invention, the support film is at least one selected from the group consisting of a polyethylene porous film, a polypropylene porous film, a polyethylene/polypropylene composite separator, a double-coated adhesive polyethylene porous film, a double-coated adhesive polypropylene porous film, a polyimide separator, and an aramid separator.
In a preferred embodiment of the present invention, the binder used in the double-coated binder polyethylene porous membrane, the double-coated binder polypropylene porous membrane is selected from at least one of polyacrylic acid (PAA), Polytetrafluoroethylene (PTFE), polyvinylidene chloride (PVDF), Polyacrylamide (PAM), styrene-butadiene rubber (SBR), Hydroxypropylmethylcellulose (HPMC), Methylcellulose (MC), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives.
According to a second aspect of the present invention, there is provided a method for preparing the above-described lithium sulfur battery separator, comprising the steps of:
and coating the nitrogen-doped carbon adsorption-conductive coating on the support film, and drying to obtain the lithium-sulfur battery diaphragm.
The preparation method of the lithium-sulfur battery diaphragm provided by the invention is simple in process, convenient to operate and suitable for industrial mass production.
In a preferred embodiment of the invention, the nitrogen-doped porous carbon-carbon nanotube-graphene and the binder are dissolved in a solvent to prepare a slurry, the slurry is coated on a support membrane, and after drying, the lithium-sulfur battery separator is obtained.
According to a third aspect of the invention, the invention provides a lithium-sulfur battery, which comprises the lithium-sulfur battery diaphragm, the sulfur positive plate and the lithium negative plate provided by the invention.
According to the lithium-sulfur battery provided by the invention, the diaphragm of the traditional microporous film structure is replaced by the diaphragm of the lithium-sulfur battery provided by the invention, the utilization rate of the active substances of the positive electrode is improved, and the transmembrane diffusion of polysulfide is limited, so that the cycle performance of the lithium-sulfur battery is improved.
In a preferred embodiment of the present invention, the sulfur positive electrode sheet is mainly prepared by coating a positive electrode material on a positive electrode current collector.
In a further preferred embodiment of the present invention, the positive electrode material includes a positive electrode active material, a conductive agent, and a binder.
In a preferred embodiment of the present invention, the positive electrode active material is a sulfur-carbon composite and/or sulfur; the conductive agent is selected from at least one of graphite, carbon black, acetylene black, graphene, carbon fiber and carbon nano tube; the binder is selected from at least one of polyacrylic acid (PAA), Polytetrafluoroethylene (PTFE), polyvinylidene chloride (PVDF), Polyacrylamide (PAM), Styrene Butadiene Rubber (SBR), hydroxypropyl methylcellulose (HPMC), Methylcellulose (MC), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), acrylonitrile copolymer, sodium alginate, chitosan and chitosan derivatives.
In a preferred embodiment of the present invention, the lithium negative electrode sheet is selected from at least one of a lithium electrode, a lithium carbon electrode, a lithium alloy electrode, or a modified coated lithium electrode.
The lithium alloy electrode includes a lithium aluminum alloy electrode, a lithium indium alloy electrode, a lithium tin alloy electrode, a lithium magnesium alloy electrode, a lithium silicon alloy electrode, and the like.
The modified coated lithium electrode comprises inorganic matter coated lithium electrode, organic matter coated lithium electrode, polymer coated lithium electrode and the like.
According to a fourth aspect of the present invention, there is provided a method of manufacturing the above lithium sulfur battery, comprising the steps of:
and placing the lithium-sulfur battery diaphragm between the sulfur positive plate and the lithium negative plate to assemble a coiled core, placing the coiled core into a lithium-sulfur battery shell, injecting electrolyte, and sealing to obtain the lithium-sulfur battery.
The preparation method of the lithium-sulfur battery provided by the invention is simple in process, convenient to operate and suitable for industrial mass production.
The technical solution provided by the present invention is further described below with reference to examples and comparative examples.
Example 1
The embodiment provides a lithium-sulfur battery diaphragm, which is formed by compounding a polypropylene porous membrane with the thickness of 25 mu m as a supporting membrane and a nitrogen-doped carbon adsorption-conductive coating with the thickness of 5 mu m, wherein the preparation method comprises the following steps:
adding the nitrogen-doped porous carbon-carbon nanotube-graphene and polyvinylidene chloride adhesive into N-methyl pyrrolidone according to the mass ratio of 9:1 to prepare slurry, then coating the slurry on the surface of a support membrane, and drying to obtain the lithium-sulfur battery diaphragm composite diaphragm.
The nitrogen-doped porous carbon-carbon nanotube-graphene is prepared by the following steps:
dispersing amino modified nano porous carbon, carboxylated single-layer graphene and carboxylated double-wall carbon nanotubes into a toluene solution according to the mass ratio of 1:2:1, adding DCC for activation, heating to 100 ℃, and refluxing for 48 hours to obtain the nitrogen-doped porous carbon-carbon nanotube-graphene.
The amino modified nanoporous carbon is prepared by the following steps:
(1) acetylene black is adopted as the nano porous carbon, and the nano porous carbon and H are mixed2SO4With HNO3Mixed solution of (2) (98% H)2SO4:68％HNO33:1, volume ratio) is mixed according to the mass ratio of 1:200-300, reflux reaction is carried out for 4h under the condition of ultrasonic oscillation at the temperature of 30-40 ℃, the mixture is cooled to room temperature, deionized water is added for dilution, suction filtration is carried out, and the filtrate is washed by the deionized water until the pH value of the filtrate is 7;
(2) placing the product of the step (1) in H2SO4And H2O2Mixed solution of (2) (98% H)2SO4:30％H2O21:4 (volume ratio)), refluxing for 0.5h at 70 ℃, filtering, washing with deionized water until the pH of the filtrate is neutral, and placing the product in a vacuum oven for vacuum drying for 24h to obtain the carboxylated nanoporous carbon;
(3) and (3) placing the product obtained in the step (2) into a reaction bottle, adding excessive thionyl chloride and an organic solvent, stirring and refluxing for 24 hours at 70 ℃, filtering, washing and drying to obtain the acyl-chlorinated nano porous carbon material.
(4) And (4) placing the product obtained in the step (3) into a reaction bottle, adding a certain amount of ethylenediamine, refluxing and stirring in an organic solvent at 75 ℃ for 48 hours, filtering, washing and drying to obtain the amino modified porous carbon.
Example 2
The embodiment provides a lithium-sulfur battery diaphragm, which is formed by compounding a polyethylene porous membrane with the thickness of 25 microns as a support membrane and a nitrogen-doped carbon adsorption-conductive coating with the thickness of 10 microns, and the preparation method of the diaphragm is the same as that of embodiment 1, except that nitrogen-doped porous carbon-carbon nanotube-graphene is prepared from amino-modified nano-porous carbon, carboxylated double-layer graphene and carboxylated single-wall carbon nanotube according to the mass ratio of 1:2:1, wherein the amino-modified nano-porous carbon adopts ketjen black and acetylene black (mass ratio of 1:1) as a nano-porous carbon material source.
Example 3
The embodiment provides a lithium-sulfur battery diaphragm, which is compounded by taking a polyethylene porous membrane with the thickness of 25 mu m and the double-side coated polyvinylidene chloride as a supporting membrane and a nitrogen-doped carbon adsorption-conductive coating with the thickness of 10 mu m, and the preparation method comprises the following steps: mixing nitrogen-doped porous carbon-carbon nanotube-graphene, styrene butadiene rubber and acrylonitrile according to a mass ratio of 94: 3: and 3, adding the mixture into a deionized water and isopropanol mixed solution (the mass ratio of the deionized water to the isopropanol is 3:1) to be mixed to prepare slurry, then coating the slurry on the surface of the support membrane, and drying to obtain the lithium-sulfur battery diaphragm.
The preparation method of the nitrogen-doped porous carbon-carbon nanotube-graphene is the same as that of the nitrogen-doped porous carbon-carbon nanotube-graphene provided in the embodiment 1, except that the amino-modified porous carbon-carbon nanotube-graphene adopts ketjen black as a porous carbon material source.
Example 4
The embodiment provides a lithium-sulfur battery diaphragm, which is compounded by taking a polyethylene porous membrane with the thickness of 25 mu m and the double-side coated polyvinylidene chloride as a supporting membrane and a nitrogen-doped carbon adsorption-conductive coating with the thickness of 10 mu m, and the preparation method comprises the following steps: mixing nitrogen-doped porous carbon-carbon nanotube-graphene, styrene butadiene rubber and carboxymethyl cellulose according to a mass ratio of 92: 5: and 3, adding the mixture into deionized water, mixing to prepare slurry, coating the slurry on the surface of the support membrane, and drying to obtain the lithium-sulfur battery diaphragm.
The preparation method of the nitrogen-doped porous carbon-carbon nanotube-graphene is the same as that of the nitrogen-doped porous carbon-carbon nanotube-graphene provided in the embodiment 1, except that mesoporous carbon (CMK-3) is adopted as a nano porous carbon material source for the amino-modified porous carbon-carbon nanotube-graphene.
Example 5
The embodiment provides a lithium-sulfur battery diaphragm, and the difference between the diaphragm provided by the embodiment and the embodiment 3 is that the nitrogen-doped porous carbon-carbon nanotube-graphene is prepared from amino-modified nano porous carbon, carboxylated double-layer graphene and carboxylated double-wall carbon nanotubes according to the mass ratio of 1:3: 1.
Example 6
The embodiment provides a lithium-sulfur battery diaphragm, and the difference between the diaphragm provided by the embodiment and the embodiment 3 is that the nitrogen-doped porous carbon-carbon nanotube-graphene is prepared from amino-modified nano porous carbon, carboxylated double-layer graphene and carboxylated double-wall carbon nanotubes according to the mass ratio of 2:3: 2.
Example 7
The embodiment provides a lithium-sulfur battery diaphragm, and the difference between the diaphragm provided by the embodiment and the embodiment 3 is that the nitrogen-doped porous carbon-carbon nanotube-graphene is prepared from amino-modified nano porous carbon, carboxylated double-layer graphene and carboxylated double-wall carbon nanotubes according to the mass ratio of 6:1: 4.
Example 8
The embodiment provides a lithium-sulfur battery diaphragm, and the difference between the diaphragm provided by the embodiment and the embodiment 3 is that the nitrogen-doped carbon adsorption-conductive coating is made of nitrogen-doped porous carbon-carbon nanotube-graphene, styrene butadiene rubber and acrylonitrile in a mass ratio of 50:25: 25.
Comparative example 1
The comparative example provides a lithium-sulfur battery separator, which is formed by compounding a polyethylene porous membrane with the thickness of 25 mu m as a support membrane and an acetylene black coating with the thickness of 10 mu m, and the preparation method comprises the following steps: adding acetylene black and vinylidene chloride into N-methyl pyrrolidone according to the mass ratio of 9:1, mixing to prepare slurry, then coating the slurry on the surface of a support film, and drying to obtain the lithium-sulfur battery diaphragm.
Comparative example 2
The comparative example provides a lithium-sulfur battery diaphragm, which is formed by compounding a polyethylene porous membrane with the thickness of 25 mu m as a support membrane and a graphene coating with the thickness of 10 mu m, and the preparation method comprises the following steps: and adding single-layer graphene and vinylidene chloride into N-methyl pyrrolidone according to the mass ratio of 9:1, mixing to prepare slurry, coating the slurry on the surface of a support film, and drying to obtain the lithium-sulfur battery diaphragm.
Comparative example 3
The comparative example provides a lithium-sulfur battery diaphragm, which is formed by compounding a polyethylene porous membrane with the thickness of 25 mu m as a supporting membrane and a carbon nano tube coating with the thickness of 10 mu m, and the preparation method comprises the following steps: and adding the double-wall carbon nano tube and vinylidene chloride into N-methyl pyrrolidone according to the mass ratio of 9:1 to prepare slurry, then coating the slurry on the surface of a support film, and drying to obtain the lithium-sulfur battery diaphragm.
Comparative example 4
This comparative example provides a lithium sulfur battery separator, a commercially available lithium sulfur battery Celgard2500 separator.
Example 9
Embodiment 9 provides a lithium sulfur pouch battery, which includes a sulfur positive plate, a lithium metal negative electrode and the lithium sulfur battery diaphragm provided in embodiment 1, the lithium sulfur battery diaphragm is placed between the sulfur positive plate and the lithium metal negative electrode, a rolled core is assembled, the rolled core is placed in a lithium sulfur battery shell, an electrolyte is injected, and sealing is performed, so as to obtain the lithium sulfur battery, wherein the electrolyte is prepared from 1mol/L lithium bis (trifluoromethyl) sulfenamide, 0.1mol/L lithium nitrate, and a mixed solution of Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (the volume ratio of the two is 1: 1); the sulfur positive plate is prepared by coating a positive material on an aluminum foil, and the positive material is prepared by mixing pure sulfur, acetylene black and polyvinylidene chloride according to a mass ratio of 8:1: 1.
Example 10
Example 10 provides a lithium sulfur pouch battery, which is different from example 9 in that the lithium sulfur battery separator provided in example 2 is used as a separator.
Example 11
Example 11 provides a lithium sulfur pouch battery, which is different from example 9 in that the lithium sulfur battery separator provided in example 3 is used as a separator.
Example 12
Example 12 provides a lithium sulfur pouch cell, which differs from example 9 in that the lithium sulfur cell separator provided in example 4 was used as a separator.
Example 13
Example 13 provides a lithium sulfur pouch battery, which differs from example 9 in that the lithium sulfur battery separator provided in example 5 is used as a separator.
Example 14
Example 14 provides a lithium sulfur pouch cell, which differs from example 9 in that the lithium sulfur cell separator provided in example 6 was used as a separator.
Example 15
Example 15 provides a lithium sulfur pouch cell, which differs from example 9 in that the lithium sulfur cell separator provided in example 7 was used as a separator.
Example 16
Example 16 provides a lithium sulfur pouch cell, which differs from example 9 in that the lithium sulfur cell separator provided in example 8 is used as a separator.
Comparative example 5
Comparative example 5 provides a lithium sulfur pouch battery, which is different from example 9 in that the lithium sulfur battery separator provided in comparative example 1 is used as a separator.
Comparative example 6
Comparative example 6 provides a lithium sulfur pouch cell, which is different from example 9 in that the lithium sulfur cell separator provided in comparative example 2 is used as a separator.
Comparative example 7
Comparative example 7 provides a lithium sulfur pouch cell, which is different from example 9 in that the lithium sulfur cell separator provided in comparative example 3 is used as a separator.
Comparative example 8
Comparative example 8 provides a lithium sulfur pouch cell, which is different from example 9 in that the lithium sulfur cell separator provided in comparative example 4 was used as a separator.
Test example 1
Scanning electron microscope analysis is performed on the nitrogen-doped porous carbon-carbon nanotube-graphene prepared in the embodiment 3, fig. 1 is a scanning electron microscope image of the nitrogen-doped porous carbon-carbon nanotube-graphene provided in the embodiment 3 of the present invention, and as shown in fig. 1, in the nitrogen-doped porous carbon-carbon nanotube-graphene, the nano porous carbon is uniformly dispersed between the carbon nanotube and the graphene, and is tightly cross-linked with the carbon nanotube and the graphene, so that no obvious agglomeration phenomenon occurs.
Test example 2
The lithium sulfur soft package battery provided in example 11 and the lithium sulfur soft package battery provided in comparative example 8 were subjected to charge and discharge performance tests, and fig. 2 is a charge and discharge curve of the lithium sulfur soft package battery provided in example 11 and the lithium sulfur soft package battery provided in comparative example 8 of the present invention; as can be seen from fig. 2, the specific discharge capacity of the lithium sulfur pouch battery provided in comparative example 8 is significantly lower than that of the lithium sulfur pouch battery provided in example 11, which shows that after the lithium sulfur battery adopts the lithium sulfur battery separator provided in the present invention, the utilization rate of the active material of the positive electrode is significantly improved, the transmembrane diffusion of polysulfide is significantly limited, and the specific discharge capacity is significantly improved.
Test example 3
The cycle performance of the lithium sulfur pouch battery provided in example 11 and the lithium sulfur pouch battery provided in comparative example 8 were tested, and fig. 3 is a cycle curve of the lithium sulfur pouch battery provided in example 11 of the present invention and the lithium sulfur pouch battery provided in comparative example 8; as can be seen from fig. 2, the discharge capacity of the lithium sulfur pouch battery provided in example 11 is significantly higher than that of the lithium sulfur pouch battery provided in comparative example 8 at the same cycle number, which indicates that after the lithium sulfur battery adopts the lithium sulfur battery separator provided in the present invention, the utilization rate of the active material of the positive electrode is significantly improved, the transmembrane diffusion of polysulfide is significantly limited, and the specific discharge capacity and the cycle performance are significantly improved.
Test example 4
Electrochemical performance of the lithium sulfur pouch cells provided in examples 9-16 and comparative examples 5-8, respectively, at a current density of 0.5C, and the test results are shown in table 1.
TABLE 1 electrochemical Performance data sheet for lithium sulfur pouch cell
As can be seen from comparison between examples 9 to 16 and comparative example 8 in table 1, after the lithium sulfur soft package battery adopts the lithium sulfur battery separator provided by the present invention, the initial specific discharge capacity and the cycle performance of the lithium sulfur soft package battery are both significantly improved compared with the commercial Celgard2500 separator, which indicates that after the lithium sulfur battery adopts the lithium sulfur battery separator provided by the present invention, the utilization rate of the positive electrode active material is significantly improved, the transmembrane diffusion of polysulfide is significantly limited, and the cycle performance of the lithium sulfur battery is significantly improved.
As can be seen from the comparison of examples 9 to 16 with comparative examples 5 to 7, the lithium sulfur battery separator made of the nitrogen-doped carbon adsorption-conductive coating made by compounding the nitrogen-doped porous carbon-carbon nanotube-graphene and the binder on the support film can effectively improve the initial specific discharge capacity and the cycle performance of the battery more than the separator made of the acetylene black coating compounded on the support film, the separator made of the carbon nanotube coating compounded on the support film and the separator made of the graphene coating compounded on the support film.
As can be seen from the comparison of examples 9-14 and example 15, the mass ratio of the nanoporous carbon, the graphene and the carbon nanotube is (1-2): (2-3): and (1-2) the lithium-sulfur diaphragm prepared from the nitrogen-doped porous carbon-carbon nanotube-graphene can improve the initial discharge specific capacity and the cycle performance of the battery.
As can be seen by comparing examples 9-14 with example 16, the mass ratio of the nitrogen-doped porous carbon-carbon nanotube-graphene to the binder is (80-99): (1-20), the prepared lithium-sulfur separator can improve the initial discharge specific capacity and the cycle performance of the battery.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (21)
1. The lithium-sulfur battery diaphragm is characterized by comprising a support film, wherein a nitrogen-doped carbon adsorption-conductive coating is compounded on the support film;
the nitrogen-doped carbon adsorption-conductive coating is mainly prepared from nitrogen-doped porous carbon-carbon nanotube-graphene and an adhesive;
the nitrogen-doped porous carbon-carbon nanotube-graphene is mainly prepared from nano porous carbon, graphene and a carbon nanotube, and the mass ratio of the nano porous carbon to the graphene to the carbon nanotube is (1-2): (2-3): (1-2);
the preparation method of the nitrogen-doped porous carbon-carbon nanotube-graphene comprises the following steps:
mixing the amino modified nano porous carbon, the carboxylated graphene and the carboxylated carbon nanotube, and carrying out condensation reaction to obtain nitrogen-doped porous carbon-carbon nanotube-graphene;
the preparation method of the amino modified nanoporous carbon comprises the following steps:
(a) carboxylating the nano porous carbon to obtain carboxylated nano porous carbon;
(b) acylating and chlorinating the carboxylated nanoporous carbon to obtain an acylchlorinated nanoporous carbon;
(c) and performing amino modification on the acyl chlorination nanoporous carbon to obtain the amino modified nanoporous carbon.
2. The lithium-sulfur battery separator according to claim 1, wherein the mass ratio of the nitrogen-doped porous carbon-carbon nanotube-graphene to the binder is (80-99): (1-20).
3. The lithium sulfur battery separator according to claim 1,
the condensation reaction is carried out under the action of an activating agent.
4. The lithium sulfur battery separator according to claim 3, wherein the activator is selected from at least one of N-hydroxysuccinimide, or 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide, or N, N' -dicyclohexylcarbodiimide.
5. The lithium-sulfur battery separator according to claim 1, wherein the preparation method of the amine-modified nanoporous carbon comprises the following steps:
in the step (a), firstly, refluxing the nano porous carbon and the mixed solution of sulfuric acid and nitric acid, then reacting the refluxed nano porous carbon and the mixed solution of sulfuric acid and hydrogen peroxide, and refluxing to obtain the carboxylated nano porous carbon.
6. The lithium-sulfur battery separator according to claim 1, wherein in step (b), the carboxylated nanoporous carbon and thionyl chloride are dissolved in an organic solvent, and reacted and refluxed to obtain the acylchlorinated nanoporous carbon.
7. The lithium-sulfur battery separator according to claim 1, wherein in step (c), the acyl chloride nanoporous carbon and ethylenediamine are dissolved in an organic solvent and reacted to obtain the amine-modified nanoporous carbon.
8. The lithium sulfur battery separator according to claim 1, wherein the nanoporous carbon is selected from at least one of ketjen black, acetylene black, mesoporous carbon, or carbon molecular sieves.
9. The lithium sulfur battery separator according to claim 1, wherein the carboxylated graphene is selected from a single layer of carboxylated graphene and/or a plurality of layers of carboxylated graphene.
10. The lithium sulfur battery separator according to claim 1, wherein the carboxylated carbon nanotubes are selected from the group consisting of single-walled carboxylated carbon nanotubes and/or multi-walled carboxylated carbon nanotubes.
11. The separator for a lithium-sulfur battery according to any one of claims 1 to 10, wherein the support film is at least one selected from a polyethylene porous film, a polypropylene porous film, a polyethylene/polypropylene composite separator, a double-coated adhesive polyethylene porous film, a double-coated adhesive polypropylene porous film, a polyimide separator, and an aramid separator.
12. The lithium sulfur battery separator according to claim 1, wherein the support film has a thickness of 16 to 25 μm.
13. The lithium sulfur battery separator according to claim 1, wherein the nitrogen-doped carbon adsorption-conductive coating has a thickness of 4 to 10 μm.
14. The method of preparing a lithium sulfur battery separator according to any one of claims 1 to 10, comprising the steps of:
and coating the nitrogen-doped carbon adsorption-conductive coating on the support film, and drying to obtain the lithium-sulfur battery diaphragm.
15. The method of preparing a lithium sulfur battery separator according to claim 14, comprising the steps of: dissolving the nitrogen-doped porous carbon-carbon nanotube-graphene and the adhesive in a solvent to prepare slurry, coating the slurry on a support membrane, and drying to obtain the lithium-sulfur battery diaphragm.
16. A lithium sulfur battery comprising the lithium sulfur battery separator according to any one of claims 1 to 13, a sulfur positive electrode sheet, and a lithium negative electrode sheet.
17. The lithium sulfur battery as recited in claim 16, wherein the sulfur positive electrode sheet is mainly prepared by coating a positive electrode material on a positive electrode current collector.
18. The lithium sulfur battery of claim 16, wherein the positive electrode material comprises a positive electrode active material, a conductive agent, and a binder.
19. The lithium sulfur battery of claim 18 wherein the positive electrode active material is sulfur-carbon composite and/or sulfur.
20. The lithium sulfur battery of claim 16 wherein the lithium negative electrode sheet is selected from at least one of a lithium electrode, a lithium carbon electrode, a copper lithium composite electrode, a lithium alloy electrode, or a modified coated lithium electrode.
21. A method of manufacturing a lithium-sulphur cell according to any of claims 16 to 20, comprising the steps of:
and placing the lithium-sulfur battery diaphragm between the sulfur positive plate and the lithium negative plate to assemble a coiled core, placing the coiled core into a lithium-sulfur battery shell, injecting electrolyte, and sealing to obtain the lithium-sulfur battery.
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| US20230183524A1 (en) * | 2020-01-15 | 2023-06-15 | South China Normal University | Polyamine composite material and preparation method therefor, slurry, separator, electrode sheet, and lithium-sulfur battery containing the same |
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