CN116376279A - Sulfur-phenylenediamine polymer composite material and preparation method and application thereof - Google Patents
Sulfur-phenylenediamine polymer composite material and preparation method and application thereof Download PDFInfo
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- CN116376279A CN116376279A CN202310190638.5A CN202310190638A CN116376279A CN 116376279 A CN116376279 A CN 116376279A CN 202310190638 A CN202310190638 A CN 202310190638A CN 116376279 A CN116376279 A CN 116376279A
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- Prior art keywords
- sulfur
- phenylenediamine
- composite material
- polymer composite
- carbon
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 31
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000011733 molybdenum Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Polymers & Plastics (AREA)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a sulfur-phenylenediamine polymer composite material, a preparation method and application thereof, wherein the method comprises the following steps: mixing elemental sulfur and phenylenediamine polymer, heating at 100-500 ℃ for reaction, and cooling to obtain sulfur-phenylenediamine polymer composite material A; wherein the phenylenediamine polymer is polymerized by taking one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine as monomers through a chemical oxidation method or an electrochemical oxidation method; and removing the elemental sulfur from the sulfur-phenylenediamine polymer composite material A through heating evaporation/sublimation or dissolution washing to obtain a sulfur-phenylenediamine polymer composite material B with reduced elemental sulfur content or completely removed elemental sulfur. The invention uses the sulfur-phenylenediamine polymer composite material as the anode material of the secondary battery, and has the advantages of low cost, high specific capacity, high coulomb efficiency, good cycle stability and the like.
Description
Technical Field
The invention relates to the technical fields of physical chemistry, organic chemistry, polymer science and material science, in particular to a preparation method and application of a sulfur-phenylenediamine polymer composite material.
Background
The existing commercial lithium ion battery system is difficult to meet the higher requirements of people on energy density, price, sustainability and the like due to the limitation of positive and negative theoretical specific capacity and metal (cobalt, nickel and lithium) resources, so that the development of a high specific energy positive electrode material and a battery system which are not limited by the resources has very important significance for the development of the fields of electric automobiles, energy storage power stations and the like. The theoretical specific capacity of elemental sulfur is highest (1672 mAh g) -1 ) The solid-state anode material of the lithium-sulfur battery can reach 2600Wh kg when being matched with a metal lithium anode to form the lithium-sulfur battery -1 The theoretical specific energy of the lithium ion battery system is 5-7 times of that of the current mainstream lithium ion battery system. In addition, the sulfur positive electrode can be matched with a metal sodium and potassium negative electrode with almost unlimited resources to form a sodium sulfur and potassium sulfur battery, and the sulfur positive electrode has more remarkable advantages in cost and sustainability although the energy density is reduced.
Currently, alkali metal-sulfur cell technology still presents a significant challenge in industrial applications, mainly related to the inherent electrochemical behavior of its system. Taking lithium sulfur cells as an example, elemental sulfur undergoes a complex solid-liquid-solid conversion during discharge: s in a voltage range of 2.4-2.1V 8 Lithium polysulfide (Li) reduced to a readily soluble organic electrolyte 2 S x X=8 to 4); in the voltage range of 2.1V and below, li 2 S x Is further reduced to insoluble solid product Li 2 S 2 And Li (lithium) 2 S, S. The lithium polysulfide intermediate product dissolved in the electrolyte can be continuously consumed by chemical or electrochemical reaction on the surface of a lithium negative electrode, or shuttle behavior occurs between the positive electrode and the negative electrode in the charging process, so that the problems of continuous attenuation of the battery capacity, reduction of coulomb efficiency, serious self-discharge and the like are caused. In addition, by S 8 Complete conversion to Li 2 S will produce a volume change of 80%Is turned into a shape, and S 8 And Li (lithium) 2 The electron and ion conductivities of S are low, so that the problems of continuous deterioration of the electrode structure, slow reaction kinetics, low capacity utilization rate, poor circulation stability and the like are caused.
In order to solve the above problems, a general strategy is to apply various carbon materials (including nitrogen-doped carbon), inorganic metal compounds, metal-organic frameworks, organic polymers, and the like as a coating layer, host material or binder of elemental sulfur in the positive electrode, and a separator modification layer by utilizing the effects of electron conduction, physical confinement, chemisorption, and chemical catalysis. Among them, the organic polymers commonly used are conductive polymers such as polyaniline (PAni), polypyrrole (PPy), polythiophene (PTh), poly (3, 4-ethylenedioxythiophene) (PEDOT) and poly (3, 4-ethylenedioxythiophene): poly (4-styrenesulfonic acid) (PEDOT: PSS) (J.Am.Chem.Soc., 2013,135:16736;Adv.Mater, 2017,29: 1700587). However, the effect of simply melt-compounding the hetero atoms in these conductive polymers with elemental sulfur is limited due to the weak adsorption capacity of the hetero atoms to lithium polysulfide, the low specific surface area, the poor uniformity of mixing, and the like. Although the limiting area and adsorption can be enhanced by increasing the weight ratio of polymer/elemental sulfur or by complex structural designs (such as coating, core-shell, lamination and the like), the methods can also obviously reduce the overall energy density of the sulfur positive electrode, greatly increase the preparation cost, still have still unsatisfactory long-term cycle stability, and therefore have limited practical application values.
Therefore, it is necessary to develop a sulfur-polymer composite positive electrode material having low cost, high specific capacity, high coulombic efficiency and good cycle stability.
Disclosure of Invention
The invention aims to provide a sulfur-phenylenediamine polymer composite material and a preparation method thereof, wherein the sulfur-phenylenediamine polymer composite material is used as a secondary battery anode material, has the advantages of low cost, high specific capacity, high coulombic efficiency, good cycle stability and the like, and can adjust the content of elemental sulfur and elemental sulfur components by controlling the feeding ratio of elemental sulfur and phenylenediamine polymer and further removing elemental sulfur according to application requirements (respectively obtaining composite materials A and B) so as to realize balance of energy density and cycle stability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method of preparing a sulfur-phenylenediamine polymer composite material comprising sulfur-phenylenediamine polymer composite material a, sulfur-phenylenediamine polymer composite material B; the method comprises the following steps:
mixing elemental sulfur and phenylenediamine polymer, heating at 100-500 ℃ for reaction, and cooling to obtain sulfur-phenylenediamine polymer composite material A; wherein the phenylenediamine polymer is polymerized by taking one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine as monomers through a chemical oxidation method or an electrochemical oxidation method;
and removing the elemental sulfur from the sulfur-phenylenediamine polymer composite material A through heating evaporation/sublimation or dissolution washing to obtain a sulfur-phenylenediamine polymer composite material B with reduced elemental sulfur content or completely removed elemental sulfur.
Further, the mass ratio of the elemental sulfur to the phenylenediamine polymer is 10:1 to 1:3.
further, the heating reaction is carried out for 1-4320 minutes at the reaction temperature of 100-500 ℃.
Further, the reaction atmosphere of the heating reaction is selected from vacuum, air, nitrogen or inert gas.
In a second aspect of the present invention, there is provided a sulfur-phenylenediamine polymer composite material prepared using the method.
In a third aspect of the present invention, there is provided a sulfur-phenylenediamine polymer composite-based derivative or multiplex composite comprising a sulfur-phenylenediamine polymer composite a-based derivative or multiplex composite and a sulfur-phenylenediamine polymer composite B-based derivative or multiplex composite;
the preparation method of the derivative or the multiple compound taking the sulfur-phenylenediamine polymer composite material as a main body comprises the steps of adding an additive into the heating reaction or compounding the reaction raw material with the additive firstly and then carrying out the heating reaction, wherein the additive comprises at least one of a carbon material, a metal compound and a chalcogen element simple substance; the carbon material is selected from conductive carbon black, active carbon, carbon nano tube, carbon fiber, graphite, graphene, hard carbon, soft carbon and porous carbon, the metal compound is selected from carbide, nitride, oxide, sulfide, phosphide, selenide, telluride and MXene, and the chalcogen element simple substance is selected from selenium and tellurium.
In a fourth aspect of the invention, there is provided the use of the sulfur-phenylenediamine polymer composite material or the derivative or multiple composite comprising the sulfur-phenylenediamine polymer composite material as a host in the preparation of a battery positive electrode.
In a fifth aspect of the present invention, there is provided a positive electrode of a battery, wherein the positive electrode is prepared by uniformly mixing and coating or pressing 30% -99% of active material, 1% -70% of conductive agent and 0% -40% of binder on a current collector, and the active material is the sulfur-phenylenediamine polymer composite material or the derivative or multiple composite based on the sulfur-phenylenediamine polymer composite material.
In a sixth aspect of the invention, a battery is provided, wherein the battery is assembled by matching a battery anode with a battery cathode directly or after pre-lithium/sodium/potassium treatment.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) The phenylenediamine polymer used in the invention is polymerized by taking o-phenylenediamine, m-phenylenediamine or p-phenylenediamine as monomers through a chemical oxidation method or an electrochemical oxidation method, and has the advantages of low raw material cost, simple synthesis method, mass production and sustainable resources.
(2) The structure of the phenylenediamine polymer used in the invention is very beneficial to realizing covalent bond compounding and solid-solid conversion reaction of sulfur: the continuous conjugated structure can provide a polymer framework with stable rigidity and favorable electron conduction; abundant benzene ring reaction sites are favorable for generating C-S x -C (x.gtoreq.2) covalent bond; the abundant pyrazine ring structure not only has adsorption and catalysis effects on sulfur species, but also contributes to extra capacity; the larger specific surface area is beneficial to improving the sulfur content and strengthening the limiting effect.
(3) The preparation method of the sulfur-phenylenediamine polymer composite material provided by the invention has the advantages of easily available raw materials, simple process, no use of organic solvents and easiness in large-scale production.
(4) The sulfur-phenylenediamine polymer composite material prepared by the method has the advantages of high specific capacity, high coulombic efficiency, good cycle stability and the like as a secondary battery anode material, and the sulfur element content and the elemental sulfur component content can be regulated by controlling the feeding ratio of elemental sulfur and phenylenediamine polymer and further removing elemental sulfur according to application requirements (respectively obtaining composite materials A and B) so as to realize balance of energy density and cycle stability.
(5) The sulfur-phenylenediamine polymer composite material prepared by the method can be applied to various alkali metal batteries such as lithium, sodium, potassium and the like, and can also be applied to corresponding ion batteries in a positive electrode or negative electrode pre-lithium/sodium/potassium mode.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are the result data of some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is (a) an X-ray diffraction spectrum and (b) a thermogravimetric curve of S-PoPDA-300-3;
FIG. 2 is a scanning electron microscope image of (a) PoPDA and (b) S-PoPDA-300-3;
fig. 3 is (a) cycle performance and (b) corresponding charge and discharge curves of S-PoPDA-300-3 in a lithium secondary battery using an ether electrolyte;
FIG. 4 is (a) an X-ray diffraction spectrum, (b) a thermogravimetric curve, (c) an infrared spectrum, and (d) a Raman spectrum of S-PoPDA-400-2 and S-PoPDA-400-3;
FIG. 5 is a scanning electron microscope image of (a) S-PoPDA-400-2 and (b) S-PoPDA-400-3;
fig. 6 is a graph showing (a, c) cycle performance and (b, d) corresponding charge and discharge curves of (a, b) S-PoPDA-400-2 and (c, d) S-PoPDA-400-3 in a lithium secondary battery using an ester electrolyte;
fig. 7 is (a) cycle performance and (b) corresponding charge and discharge curves of S-PoPDA-400-2 in a lithium secondary battery using an ether electrolyte;
fig. 8 is (a) cycle performance and (b) corresponding charge and discharge curves of S-PoPDA-400-2 in a sodium secondary battery using an ester electrolyte;
FIG. 9 is a graph showing (a) cycle performance and (b) corresponding charge and discharge curves of S-PoPDA-400-2 in a potassium secondary battery using an ester electrolyte;
fig. 10 is (a) cycle performance and (b) corresponding charge and discharge curves of S-PmPDA-400-10 in a lithium secondary battery using an ester electrolyte;
FIG. 11 is a graph showing (a) cycle performance and (b) corresponding charge and discharge curves of S-PmPDA-400-10 in a sodium secondary battery using an ester electrolyte;
FIG. 12 is a graph showing (a) cycle performance and (b) corresponding charge-discharge curves of S-PmPDA-400-10 in a potassium secondary battery using an ester electrolyte;
FIG. 13 is a graph showing (a) cycle performance and (b) corresponding charge and discharge curves of S-PpPDA-400-10 in a lithium secondary battery using an ester electrolyte;
FIG. 14 is (a) cycle performance and (b) corresponding charge and discharge curves of S-PpPDA-400-10 in a sodium secondary battery using an ester electrolyte;
FIG. 15 is a graph showing (a) cycle performance and (b) corresponding charge and discharge curves of S-PpPDA-400-10 in a potassium secondary battery using an ester electrolyte;
fig. 16 is (a) cycle performance and (b) corresponding charge and discharge curves of SSe-PoPDA-400-111 in a lithium secondary battery using an ester electrolyte.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, etc., used in the present invention are commercially available or may be obtained by existing methods.
According to an exemplary embodiment of the present invention, there is provided a method of preparing a sulfur-phenylenediamine polymer composite material including sulfur-phenylenediamine polymer composite material a, sulfur-phenylenediamine polymer composite material B; the method comprises the following steps:
s101, mixing elemental sulfur and phenylenediamine polymer, heating at 100-500 ℃ for reaction, and cooling to obtain a sulfur-phenylenediamine polymer composite material A; wherein the phenylenediamine polymer is polymerized by taking one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine as monomers through a chemical oxidation method or an electrochemical oxidation method.
In the step S101 of the above-mentioned process,
the mass ratio of elemental sulfur to phenylenediamine polymer is 10:1 to 1:3. the mass ratio range is beneficial to considering the energy density and the circulation stability, if the elemental sulfur is excessively added, the adverse effect of reducing the circulation stability is caused, and if the phenylenediamine polymer is excessively added, the adverse effect of reducing the energy density and increasing the cost is caused; the mass ratio is preferably 6:1 to 1:2.
the mixing mode of the elemental sulfur and the phenylenediamine polymer is stacking, stirring, grinding, ball milling, sand grinding or solid (polymer) -liquid (elemental sulfur solution) mixing.
The reaction vessel used for the heating reaction is in a sealed or semi-sealed state, with or without vibration and rotation, and with or without stirring of reactants.
The reaction atmosphere of the heating reaction is vacuum, air, nitrogen or inert gas.
The heating mode is heating furnace heating, oil/sand bath heating or microwave heating.
The reaction temperature of the heating reaction is 100-500 ℃ and the reaction time is 1-4320 minutes. The heating procedure is a constant or varying temperature and time over a range. The reaction temperature is preferably 200 to 450 ℃, and the reaction time is preferably 60 to 1440 minutes.
And step S102, removing the contained elemental sulfur from the sulfur-phenylenediamine polymer composite material A through heating evaporation/sublimation or dissolution washing to obtain a sulfur-phenylenediamine polymer composite material B with reduced elemental sulfur content or completely removed elemental sulfur.
In the step S102 of the above-mentioned process,
for removing elemental sulfur contained in the composite material by heating evaporation/sublimation, the heating temperature is 100-500 ℃, the heating time is 1-2880 minutes, and the heating atmosphere is vacuum, air, nitrogen or inert gas. The heating temperature is preferably 200-400 ℃, the heating time is preferably 30-720 minutes, and the heating atmosphere is preferably vacuum or nitrogen.
For the way of removing elemental sulfur contained in the composite material by dissolution and washing, the washing liquid includes, but is not limited to, non-polar solvents such as benzene, toluene, carbon tetrachloride, carbon disulfide, and the like, and hot alkali solutions such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.
Compared with the composite material A obtained in the step S101, the elemental sulfur content of the obtained product sulfur-phenylenediamine polymer composite material B is obviously reduced or even zero, which can reduce the specific capacity but is beneficial to improving the coulomb efficiency and the cycle stability.
As an alternative embodiment, an additive is added in the heating reaction in the step S101 or the reaction raw material is first compounded with the additive and then subjected to the heating reaction, and other preparation processes are the same as those in the steps S101 and S102, so as to prepare a derivative or multiple composite mainly comprising the sulfur-phenylenediamine polymer composite.
Additives are added to alter/improve the physicochemical properties (e.g., electron conductivity) of the composite material, including at least one of carbon materials, metal compounds, and elemental chalcogenides; the carbon material is selected from conductive carbon black, active carbon, carbon nano tube, carbon fiber, graphite, graphene, hard carbon, soft carbon and porous carbon, the metal compound is selected from carbide, nitride, oxide, sulfide, phosphide, selenide, telluride and MXene, and the chalcogen element simple substance is selected from selenium and tellurium.
The invention also provides application of the prepared sulfur-phenylenediamine polymer composite material or the derivative or multiple composite taking the sulfur-phenylenediamine polymer composite material as a main body in secondary alkali metal (lithium, sodium and potassium) batteries and alkali metal ion batteries, and a preparation method of a corresponding positive electrode and a corresponding battery.
According to another exemplary embodiment of the present invention, there is provided a battery positive electrode, which is prepared by:
step S201, dispersing and mixing the active material, the conductive agent and the binder in a solvent according to a certain proportion, and optionally adopting dry mixing without adding the solvent; the active material is the sulfur-phenylenediamine polymer composite material or the derivative or multiple composite taking the sulfur-phenylenediamine polymer composite material as a main body; the weight percentages of the components are as follows: 30-99% of active material, 1-70% of conductive agent, 0-40% of adhesive and 100% of the total of the three.
In the step S201 of the above-mentioned process,
the conductive agent is any one or a mixture of a plurality of graphite, conductive carbon black, acetylene black, super P, ketjen black, carbon nano tube, carbon fiber, active carbon, graphene (reduced graphene oxide) and fullerene. The conductive agent is preferably conductive carbon black, acetylene black, super P, ketjen black or carbon nanotubes.
The binder is one or a mixture of more of polytetrafluoroethylene or copolymer thereof, polyvinylidene fluoride or copolymer thereof, polyethylene oxide or copolymer thereof, polyvinyl alcohol or copolymer thereof, sodium carboxymethyl cellulose, styrene-butadiene rubber or copolymer thereof, polyether or copolymer thereof, polyester or copolymer thereof and polyacrylic acid or polyacrylate. The binder is preferably polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, sodium polyacrylate or lithium polyacrylate.
The solvent is any one or a mixture of more than one of water, ethanol, methanol, propanol, isopropanol, N-butanol, N-methylpyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, dimethyl sulfoxide, sulfolane and caprolactam. The solvent is preferably water, ethanol, isopropanol or N-methylpyrrolidone.
In step S202, the mixture is coated on a current collector or pressed on the current collector after rolling, and dried to form an electrode, for example, dry mixing is used, or drying is not used.
In the step S202 of the above-mentioned process,
the current collector is made of any one of aluminum, copper, nickel, titanium, molybdenum, stainless steel and carbon, and is in the form of any one of foil (sheet), net, fiber paper and foam metal. The current collector is preferably an aluminum mesh or foil.
The drying temperature is constant or variable between 20 and 200 ℃, and the drying atmosphere is any one of vacuum, air, nitrogen, argon and helium.
According to another exemplary embodiment of the present invention, a battery is provided, wherein the battery is assembled by matching a battery anode with a battery cathode directly or after pre-lithium/sodium/potassium treatment. The preparation method of the corresponding battery comprises the following steps:
the method 1 comprises the steps of matching the positive electrode of the battery with a metal lithium/sodium/potassium negative electrode or a lithium/sodium/potassium-containing alloy negative electrode, separating the two electrodes by a diaphragm, adding electrolyte, and assembling the battery in an inert atmosphere.
The diaphragm is a composite diaphragm formed by any one or more of polyethylene, polypropylene, polytetrafluoroethylene or copolymers thereof, polyimide, cellulose and glass fiber diaphragms, and a modified diaphragm based on the diaphragms. The separator is preferably a polypropylene separator or a glass fiber separator.
The electrolyte is a solution prepared by dissolving corresponding metal (lithium, sodium and potassium) salts in a solvent, and the salt concentration is 0.1-5.0 mol L –1 . Wherein the salt is any one or a mixture of a plurality of perchlorate, hexafluorophosphate, tetrafluoroborate, trifluoromethanesulfonate, bisoxalato borate, difluorooxalato borate, bisfluorosulfonyl imide salt and bis (trifluoromethanesulfonyl) imide salt. Wherein the solvent is any one or a mixture of more than one of ethylene carbonate, vinylene carbonate, fluoroethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1, 3-dioxolane, 1, 4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyvinyl alcohol oligomer, acetonitrile, sulfolane, dimethyl sulfoxide and gamma-butyrolactone.
The inert atmosphere is any one or a mixture of more than one of nitrogen, argon and helium. The atmosphere is preferably argon.
And 2, matching the positive electrode of the battery with negative electrodes such as graphite, silicon, carbon/silicon, hard carbon, soft carbon and the like to assemble the battery, wherein the positive electrode or the negative electrode is required to be subjected to chemical or electrochemical pre-lithium/sodium/potassium treatment, so that one of the positive electrode and the negative electrode is changed from an oxidation state without lithium/sodium/potassium to a lithium/sodium/potassium intercalation reduction state. The method of pre-lithiation/sodium/potassium treatment includes a chemical method of bringing an electrode into contact with a lithium/sodium/potassium metal or metal organic reagent to cause oxidation-reduction reaction, and an electrochemical method of pre-discharging an electrode in an electrochemical device. Other preparation processes are the same as described in method 1.
The chemical pre-lithium/sodium/potassium metal organic reagent is an aromatic hydrocarbon solution such as biphenyl, naphthalene and the like in which lithium/sodium/potassium is dissolved.
The electrolyte and the negative electrode used in the electrochemical pre-lithium/sodium/potassium device are the same as those in the method 1, and the atmosphere is any one or a mixture of more of nitrogen, argon and helium.
The sulfur-phenylenediamine polymer composite material or the derivative or multiple composite based on the sulfur-phenylenediamine polymer composite material can also be applied to solid state batteries using solid state electrolytes including inorganic solid state electrolytes, solid state polymer electrolytes and composite polymer electrolytes, including all-solid state batteries entirely without using a liquid electrolyte and semi-solid and quasi-solid state batteries partially using a liquid electrolyte.
A sulfur-phenylenediamine polymer composite material of the present application, and a method for producing the same and use thereof will be described in detail with reference to examples, comparative examples and experimental data.
The monomers of the phenylenediamine polymers [ o-phenylenediamine (oPDA), m-phenylenediamine (mPDA) and p-phenylenediamine (pPDA) ] used in the present invention [ poly-o-phenylenediamine (PoPDA), poly-m-phenylenediamine (PmPDA) and p-phenylenediamine (pPDA) ] are all commercially available and no further purification is required. Phenylenediamine polymers can be synthesized by various chemical and electrochemical oxidation methods, and a large number of documents report that the yield is high.
Example 1
The preparation method of the sulfur-phenylenediamine polymer composite material and the application thereof in the secondary battery provided by the embodiment comprise the following steps in sequence:
(1) According to the mass ratio of 3:1, weighing elemental sulfur and poly-o-phenylenediamine, grinding and mixing, and then placing the mixture in a glass tube with one end closed.
(2) Pumping the glass tube filled with the reaction raw materials in the step (1) to the air pressure of less than 0.1MPa, and performing fusion tube sealing under butane flame.
(3) And (3) heating the closed glass tube filled with the reaction raw materials in the step (2) to 300 ℃, reacting for 10 hours at constant temperature, and cooling to obtain the sulfur-poly-o-phenylenediamine composite material, which is named as S-PoPDA-300-3. The X-ray diffraction spectrum is shown in figure 1a, the thermogravimetric curve is shown in figure 1b, and the microscopic morphology is shown in figure 2b (figure 2a is the morphology of the raw material PoPDA). The elemental analysis results of S-PoPDA-300-3 and the raw material PoPDA are shown in Table 1.
(4) Mixing the S-PoPDA-300-3 obtained in the step (3) with a conductive agent ketjen black and a binder polyvinyl alcohol according to the following ratio of 7:2:1, mixing water/isopropanol mixture as solvent to form slurry, coating the slurry on an aluminum foil, drying and cutting the slurry into round electrode plates with proper diameters.
(5) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal lithium sheet as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dripping a proper amount of electrolyte [1mol L ] -1 Lithium bis (trifluoromethanesulfonyl) imideSolutions of 1, 3-dioxolane/ethylene glycol dimethyl ether mixtures, i.e. 1M LiTFSI/DOL-DME]The CR2016 type coin cell was assembled in an argon-filled glove box.
(6) The battery prepared in the step (5) is charged with 200mA g in the voltage range of 1.5-3.5V -1 The activation was carried out at a current density of (based on the mass of sulfur element) 5 weeks after charging and discharging, and then at 1000mA g -1 Charge and discharge cycles were performed at a current density (based on the mass of elemental sulfur). The electrochemical performance is shown in figure 3, and the activated S-PoPDA-300-3 shows 717mAh g under high current -1 The reversible specific capacity (based on the mass of elemental sulfur) after 300 weeks of cycling was 83% capacity retention (relative to the reversible specific capacity), and the charge-discharge curve exhibited typical solid-liquid-solid conversion characteristics.
TABLE 1 elemental analysis results (wt%) for PoPDA and S-PoPDA-300-3
Example 2
The preparation method of the sulfur-phenylenediamine polymer composite material and the application thereof in the secondary battery provided by the embodiment comprise the following steps in sequence:
(1) The mass ratio is 2:1 and 3:1, weighing elemental sulfur and poly-o-phenylenediamine, grinding and mixing, and then placing the mixture in a stainless steel reaction kettle, wherein the reaction kettle is in a semi-sealing state (a threaded kettle cover is screwed, but gas still can escape).
(2) And (3) placing the stainless steel reaction kettle with the reaction raw materials in the step (1) in a tubular furnace with one end filled with nitrogen, and introducing sodium hydroxide aqueous solution into the other end of the tubular furnace for tail gas treatment.
(3) Heating the tubular furnace to 400 ℃, reacting for 5 hours at constant temperature, cooling, washing the obtained solid with toluene and ethanol in sequence, and drying at 80 ℃ to obtain the sulfur-poly-o-phenylenediamine composite material. According to the feeding mass ratio of sulfur and poly-o-phenylenediamine, the products are named as S-PoPDA-400-2 and S-PoPDA-400-3 respectively. The X-ray diffraction spectrum of the two products is shown in figure 4a, the thermogravimetric curve is shown in figure 4b, the infrared spectrum is shown in figure 4c, the Raman spectrum is shown in figure 4d, and the microscopic morphology is shown in figures 5a and 5 b. The elemental analysis results of the two products and the starting material popa are shown in table 2.
(4) Mixing the sulfur-poly-o-phenylenediamine composite material (S-PoPDA-400-2 or S-PoPDA-400-3) obtained in the step (3) with a conductive agent ketjen black and a binder polytetrafluoroethylene according to the following 6:3:1, mixing the water/isopropanol mixture serving as a solvent into a plasticine shape, rolling the plasticine shape on a pair roller to form a film, drying, cutting into small discs with proper diameters, and pressing the small discs on an aluminum mesh current collector to prepare the electrode plate.
(5) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal lithium sheet as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Solution of lithium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixture, 1M LiPF 6 EC-DEC), a CR2016 type coin cell was assembled in an argon filled glove box.
(6) The battery prepared in the step (5) is charged with 100mA g in the voltage range of 1.0-3.0V -1 The charge-discharge cycle is performed at a current density (based on the mass of the composite material, the same applies below). The electrochemical properties are shown in FIG. 6, S-PoPDA-400-2 and S-PoPDA-400-3 show 589 and 755mAh g, respectively -1 The reversible specific capacity (based on the mass of the composite material, the same applies hereinafter) after 100 weeks of cycling the capacity retention was 92% and 69% (relative to the reversible specific capacity, the same applies hereinafter) respectively, and the charge-discharge curves all exhibited typical solid-solid conversion characteristics.
(7) Taking the S-PoPDA-400-2 electrode plate prepared in the step (4) as an anode, taking a metal lithium plate as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dropwise adding a proper amount of electrolyte [1mol L ] -1 Solution of lithium bis (trifluoromethanesulfonyl) imide in 1, 3-dioxolane/ethylene glycol dimethyl ether mixture, 1M LiTFSI/DOL-DME]The CR2016 type coin cell was assembled in an argon-filled glove box.
(8) The battery prepared in the step (7) is heated to 100mAg in the voltage range of 1.0-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 7, and S-PoPDA-400-2 shows 649mAh g -1 Is a reversible ratio of (2)Capacity, after 50 weeks of cycling, capacity retention was 80%.
(9) Taking the S-PoPDA-400-2 electrode plate prepared in the step (4) as an anode, taking a metal sodium plate as a cathode, taking a combination of a polypropylene film (Celgard 2325) and a glass fiber film as a diaphragm, and dripping a proper amount of electrolyte [1mol L ] -1 Solutions of sodium bis (trifluoromethanesulfonyl) imide in ethylene carbonate/diethyl carbonate mixtures, i.e. 1M NaTFSI/EC-DEC]The CR2025 type coin cell was assembled in an argon-filled glove box.
(10) The battery prepared in the step (9) is charged with 100mAg in the voltage range of 0.8-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 8, S-PoPDA-400-2 shows 548mAh g in sodium cell -1 The capacity retention after 30 weeks of cycling was 92%.
(11) Taking the S-PoPDA-400-2 electrode plate prepared in the step (4) as an anode, taking a metal potassium plate as a cathode, taking a combination of a polypropylene film (Celgard 2325) and a glass fiber film as a diaphragm, and dripping a proper amount of electrolyte (1 mol L -1 Solutions of potassium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixtures, i.e. 1M KPF 6 EC-DEC), a CR2025 type button cell was assembled in a glove box filled with argon.
(12) The battery prepared in the step (11) is charged with 100mAg in the voltage range of 1.0-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 9, S-PoPDA-400-2 shows 295mAh g in potassium cell -1 The capacity retention after 30 weeks of cycling was 76%.
TABLE 2 elemental analysis results (wt%) for PoPDA, S-PoPDA-400-2 and S-PoPDA-400-3
Example 3
The preparation method of the sulfur-phenylenediamine polymer composite material and the application thereof in the secondary battery provided by the embodiment comprise the following steps in sequence:
(1) The mass ratio is 10:1, weighing elemental sulfur and poly-m-phenylenediamine, grinding and mixing, and then placing the mixture in a stainless steel reaction kettle, wherein the reaction kettle is in a semi-sealing state (a threaded kettle cover is screwed, but gas still can escape).
(2) And (3) placing the stainless steel reaction kettle with the reaction raw materials in the step (1) in a tubular furnace with one end filled with nitrogen, and introducing sodium hydroxide aqueous solution into the other end of the tubular furnace for tail gas treatment.
(3) Heating the tubular furnace to 400 ℃, reacting for 5 hours at constant temperature, cooling, washing the obtained solid with toluene and ethanol in sequence, and drying at 80 ℃ to obtain the sulfur-poly m-phenylenediamine composite material named S-PmPDA-400-10.
(4) Mixing the S-PmPDA-400-10 obtained in the step (3) with a conductive agent ketjen black and a binder polytetrafluoroethylene according to the following ratio of 6:3:1, mixing the water/isopropanol mixture serving as a solvent into a plasticine shape, rolling the plasticine shape on a pair roller to form a film, drying, cutting into small discs with proper diameters, and pressing the small discs on an aluminum mesh current collector to prepare the electrode plate.
(5) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal lithium sheet as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Solution of lithium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixture, 1M LiPF 6 EC-DEC), a CR2016 type coin cell was assembled in an argon filled glove box.
(6) The battery prepared in the step (5) is heated to 100mAg in the voltage range of 1.0-3.0V -1 The charge-discharge cycle is performed at a current density (based on the mass of the composite material, the same applies below). The electrochemical properties are shown in FIG. 10, and S-PmPDA-400-10 shows 475mAh g -1 The reversible specific capacity (based on the mass of the composite material, the same applies hereinafter) after 50 weeks of cycling the capacity retention was 96% (relative to the reversible specific capacity, the same applies hereinafter), and the charge-discharge curve exhibited typical solid-solid conversion characteristics.
(7) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal sodium sheet as a cathode, taking a combination of a polypropylene film (Celgard 2325) and a glass fiber film as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Sodium hexafluorophosphate in ethylene carbonateSolutions of ester/diethyl carbonate mixtures, i.e. 1M NaPF 6 EC-DEC), a CR2025 type button cell was assembled in a glove box filled with argon.
(8) The battery prepared in the step (7) is charged with 100mA g in the voltage range of 0.8-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 11, S-PmPDA-400-10 shows 440mAh g in sodium cell -1 The capacity retention after 30 weeks of cycling was 92%.
(9) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal potassium sheet as a cathode, taking a combination of a polypropylene film (Celgard 2325) and a glass fiber film as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Solutions of potassium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixtures, i.e. 1M KPF 6 EC-DEC), a CR2025 type button cell was assembled in a glove box filled with argon.
(10) The battery prepared in the step (9) is charged with 100mA g in the voltage range of 0.8-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 12, S-PmPDA-400-10 shows 455mAh g in potassium cell -1 The capacity retention after 30 weeks of cycling was 51%.
Example 4
The preparation method of the sulfur-phenylenediamine polymer composite material and the application thereof in the secondary battery provided by the embodiment comprise the following steps in sequence:
(1) The mass ratio is 10:1, weighing elemental sulfur and poly-p-phenylenediamine, grinding and mixing, and then placing the mixture in a stainless steel reaction kettle, wherein the reaction kettle is in a semi-sealing state (a threaded kettle cover is screwed, but gas still can escape).
(2) And (3) placing the stainless steel reaction kettle with the reaction raw materials in the step (1) in a tubular furnace with one end filled with nitrogen, and introducing sodium hydroxide aqueous solution into the other end of the tubular furnace for tail gas treatment.
(3) Heating a tube furnace to 400 ℃, reacting at constant temperature for 5 hours, cooling, washing the obtained solid with toluene and ethanol in sequence, and drying at 80 ℃ to obtain the sulfur-poly-p-phenylenediamine composite material named S-PpPDA-400-10.
(4) Mixing the S-PpPDA-400-10 obtained in the step (3) with a conductive agent ketjen black and a binder polytetrafluoroethylene according to a ratio of 6:3:1, mixing the water/isopropanol mixture serving as a solvent into a plasticine shape, rolling the plasticine shape on a pair roller to form a film, drying, cutting into small discs with proper diameters, and pressing the small discs on an aluminum mesh current collector to prepare the electrode plate.
(5) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal lithium sheet as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Solution of lithium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixture, 1M LiPF 6 EC-DEC), a CR2016 type coin cell was assembled in an argon filled glove box.
(6) The battery prepared in the step (5) is charged with 200mA g in the voltage range of 1.0-3.0V -1 The charge-discharge cycle is performed at a current density (based on the mass of the composite material, the same applies below). The electrochemical properties are shown in FIG. 13, S-PpPDA-400-10 shows 574mAh g -1 The reversible specific capacity (based on the mass of the composite, the same applies hereinafter) after 50 weeks of cycling the capacity retention was 84% (relative to the reversible specific capacity, the same applies hereinafter) and the charge-discharge curve exhibited typical solid-solid conversion characteristics.
(7) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal sodium sheet as a cathode, taking a combination of a polypropylene film (Celgard 2325) and a glass fiber film as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Sodium hexafluorophosphate in solution in ethylene carbonate/diethyl carbonate mixture, 1M NaPF 6 EC-DEC), a CR2025 type button cell was assembled in a glove box filled with argon.
(8) The battery prepared in the step (7) is charged with 100mA g in the voltage range of 0.8-3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 14, S-PpPDA-400-10 shows 513mAh g in sodium cell -1 The capacity retention after 30 weeks of cycling was 60%.
(9) The electrode sheet prepared in the step (4) is taken as an anode, a metal potassium sheet is taken as a cathode, and a polypropylene film (Celgard 2325) and a glass fiber film are combined to form a separatorFilm, drop-in proper amount of electrolyte (1 mol L) -1 Solutions of potassium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixtures, i.e. 1M KPF 6 EC-DEC), a CR2025 type button cell was assembled in a glove box filled with argon.
(10) The battery prepared in the step (9) is charged with 100mA g in the voltage range of 1.0 to 3.0V -1 Is subjected to charge-discharge cycles. The electrochemical properties are shown in FIG. 15, S-PpPDA-400-10 shows 293mAh g in potassium cell -1 The capacity retention after 30 weeks of cycling was 68%.
Example 5
The preparation method of the sulfur-phenylenediamine polymer composite material and the application thereof in the secondary battery provided by the embodiment comprise the following steps in sequence:
(1) According to the mass ratio of 1:1:1, weighing elemental sulfur, elemental selenium and poly-o-phenylenediamine, grinding and mixing, and then placing the mixture in a stainless steel reaction kettle, wherein the reaction kettle is in a semi-sealing state (a threaded kettle cover is screwed, but gas still can escape).
(2) And (3) placing the stainless steel reaction kettle with the reaction raw materials in the step (1) in a tubular furnace with one end filled with nitrogen, and introducing sodium hydroxide aqueous solution into the other end of the tubular furnace for tail gas treatment.
(3) Heating the tubular furnace to 400 ℃, reacting for 5 hours at constant temperature, cooling, washing the obtained solid with toluene and ethanol in sequence, and drying at 80 ℃ to obtain the selenium sulfide-poly-o-phenylenediamine composite material named SSe-PoPDA-400-111.
(4) Mixing SSe-PoPDA-400-111 obtained in the step (3) with a conductive agent ketjen black and a binder polytetrafluoroethylene according to a ratio of 6:3:1, mixing the water/isopropanol mixture serving as a solvent into a plasticine shape, rolling the plasticine shape on a pair roller to form a film, drying, cutting into small discs with proper diameters, and pressing the small discs on an aluminum mesh current collector to prepare the electrode plate.
(5) Taking the electrode sheet prepared in the step (4) as an anode, taking a metal lithium sheet as a cathode, taking a polypropylene film (Celgard 2325) as a diaphragm, and dripping a proper amount of electrolyte (1 mol L) -1 Solution of lithium hexafluorophosphate in ethylene carbonate/diethyl carbonate mixture, i.e1M LiPF 6 EC-DEC), a CR2016 type coin cell was assembled in an argon filled glove box.
(6) The battery prepared in the step (5) is charged with 100mA g in the voltage range of 1.0-3.0V -1 The charge-discharge cycle is performed at a current density (based on the mass of the composite). The electrochemical properties are shown in FIG. 16, SSe-PoPDA-400-111 shows 454mAh g -1 The capacity retention (based on the mass of the composite) was 89% (relative to the reversible specific capacity) over a 50 week cycle, and the charge-discharge curve exhibited typical solid-solid conversion characteristics.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (10)
1. A preparation method of a sulfur-phenylenediamine polymer composite material, which is characterized in that the sulfur-phenylenediamine polymer composite material comprises a sulfur-phenylenediamine polymer composite material A and a sulfur-phenylenediamine polymer composite material B; the method comprises the following steps:
mixing elemental sulfur and phenylenediamine polymer, heating at 100-500 ℃ for reaction, and cooling to obtain sulfur-phenylenediamine polymer composite material A; wherein the phenylenediamine polymer is polymerized by taking one or more of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine as monomers through a chemical oxidation method or an electrochemical oxidation method;
and removing the elemental sulfur from the sulfur-phenylenediamine polymer composite material A through heating evaporation/sublimation or dissolution washing to obtain a sulfur-phenylenediamine polymer composite material B with reduced elemental sulfur content or completely removed elemental sulfur.
2. The preparation method according to claim 1, wherein the mass ratio of elemental sulfur to phenylenediamine polymer is 10:1 to 1:3.
3. the method according to claim 1, wherein the heating reaction is carried out at a reaction temperature of 100 to 500 ℃ for 1 to 4320 minutes.
4. The method according to claim 1, wherein the reaction atmosphere of the heating reaction is selected from vacuum, air, nitrogen, or inert gas.
5. A sulfur-phenylenediamine polymer composite material produced by the production process according to any one of claims 1 to 4.
6. A derivative or multiple composite based on a sulfur-phenylenediamine polymer composite material, characterized in that the preparation method of the derivative or multiple composite is to add an additive into the heating reaction according to any one of claims 1-4 or to compound the reaction raw material with the additive first and then to carry out the heating reaction, wherein the additive comprises at least one of a carbon material, a metal compound and a chalcogen element simple substance; the carbon material is selected from conductive carbon black, active carbon, carbon nano tube, carbon fiber, graphite, graphene, hard carbon, soft carbon and porous carbon, the metal compound is selected from carbide, nitride, oxide, sulfide, phosphide, selenide, telluride and MXene, and the chalcogen element simple substance is selected from selenium and tellurium.
7. Use of the sulfur-phenylenediamine polymer composite of claim 5 or the sulfur-phenylenediamine polymer composite-based derivative or multiplex composite of claim 6 in the preparation of a battery positive electrode.
8. The positive electrode of the battery is characterized in that the positive electrode is prepared by uniformly mixing and coating or pressing 30-99% of active material, 1-70% of conductive agent and 0-40% of binder on a current collector in percentage by mass, wherein the active material is the sulfur-phenylenediamine polymer composite material of claim 5 or the derivative or multiple composite taking the sulfur-phenylenediamine polymer composite material as a main body.
9. The battery positive electrode according to claim 8, wherein the conductive agent comprises any one or a mixture of several of graphite, conductive carbon black, acetylene black, super P, ketjen black, carbon nanotubes, carbon fibers, activated carbon, graphene (reduced graphene oxide), and fullerenes; the binder comprises polytetrafluoroethylene or copolymer thereof, polyvinylidene fluoride or copolymer thereof, polyethylene oxide or copolymer thereof, polyvinyl alcohol or copolymer thereof, sodium carboxymethyl cellulose matched with styrene-butadiene rubber or copolymer thereof, polyether or copolymer thereof, polyester or copolymer thereof and any one or a mixture of more than one of polyacrylic acid or polyacrylate.
10. A battery, characterized in that the battery is assembled by matching the positive electrode of the battery in claim 8 or 9 with the negative electrode of the battery directly or after pre-lithium/sodium/potassium treatment.
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