CN112759874B - Preparation method of Se-doped sulfurized polyacrylonitrile material - Google Patents

Preparation method of Se-doped sulfurized polyacrylonitrile material Download PDF

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CN112759874B
CN112759874B CN202110016914.7A CN202110016914A CN112759874B CN 112759874 B CN112759874 B CN 112759874B CN 202110016914 A CN202110016914 A CN 202110016914A CN 112759874 B CN112759874 B CN 112759874B
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polyacrylonitrile
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CN112759874A (en
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孙永明
王伶月
段祥瑞
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Huazhong University of Science and Technology
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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
    • 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
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium secondary batteries, and discloses a preparation method of Se-doped sulfurized polyacrylonitrile material, which comprises the steps of mixing Polyacrylonitrile (PAN), a simple substance S and a simple substance Se to form a mixture, and carrying out heat treatment in a closed environment, thereby obtaining the Se-doped sulfurized polyacrylonitrile material by one step; wherein the heat treatment temperature is 250-380 ℃, and the heat treatment time is 1-24 h. According to the invention, the environment and atmosphere, reaction raw materials, reaction mechanism and the like of the preparation method are improved, S, Se and PAN are directly used as raw materials, and the synthesis is carried out by one-step heat treatment in a closed environment (such as closed air).

Description

Preparation method of Se-doped sulfurized polyacrylonitrile material
Technical Field
The invention belongs to the technical field of lithium secondary batteries, and particularly relates to a preparation method of a Se-doped polyacrylonitrile sulfide material.
Background
With the increasing demand of people for advanced energy storage technology, the research of lithium ion batteries is more and more extensive. The energy density of the traditional lithium ion battery is close to the theoretical upper limit, and the increasingly enhanced energy density requirement in the field of power batteries is difficult to meet.
The polyacrylonitrile Sulfide (SPAN) anode material has high theoretical specific capacity, good chemical compatibility with commercial carbonate electrolyte and high coulombic efficiency, and can be matched with lithium metal to construct a high specific energy lithium secondary battery. But one of the main problems inhibiting its commercial application is the slow kinetics of the electrochemical reaction and the poor rate capability at high areal loading. Researches show that after Se is doped to replace part of S in SPAN, the electronic conductivity and the ionic conductivity of the formed material are greatly improved, fast electrochemical reaction kinetics are shown, and the rate capability of the battery material is greatly improved.
Although relevant reports of Se-doped SPAN materials exist in the prior art, the preparation process steps of the prior art are complicated, the experimental environment conditions are harsh, heat treatment needs to be carried out under the flowing argon condition, the sulfur utilization rate is low, the yield is low, and the commercial production is difficult to realize.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, an object of the present invention is to provide a method for preparing Se-doped sulfurized polyacrylonitrile, wherein the environment and atmosphere, reaction raw materials, reaction mechanism, etc. of the preparation method are improved, S, Se and PAN are directly used as raw materials, and the materials are synthesized by one-step heat treatment in a closed environment (such as closed air). In addition, the obtained Se-doped sulfurized polyacrylonitrile material has good electronic conductivity and ionic conductivity, and compared with an undoped SPAN material, the Se-doped sulfurized polyacrylonitrile material improves the electrochemical reaction kinetics and improves the cycling stability of the electrode under high surface loading.
In order to achieve the purpose, the invention provides a preparation method of Se-doped sulfurized polyacrylonitrile material, which is characterized in that Polyacrylonitrile (PAN) is mixed with a simple substance S and a simple substance Se to form a mixture, and the mixture is subjected to heat treatment in a closed environment, so that the Se-doped sulfurized polyacrylonitrile material is prepared in one step; wherein the heat treatment temperature is 250-380 ℃, and the heat treatment time is 1-24 h.
In a further preferred embodiment of the present invention, the mixture contains elemental Se in an amount of 1 to 30% by mass based on the sum of elemental S and elemental Se.
In a further preferred embodiment of the present invention, the mixture contains the elemental Se in an amount of 5 to 10% by mass based on the sum of the elemental Se and the elemental Se.
In a further preferred embodiment of the present invention, in the mixture, the mass ratio of the polyacrylonitrile PAN to the mass sum of the simple substance S and the simple substance Se satisfies 1/(1.5 to 3).
In a further preferred embodiment of the present invention, in the mixture, the mass ratio of the polyacrylonitrile PAN to the mass sum of the simple substance S and the simple substance Se satisfies 1/(1.65 to 1.85).
In a further preferred embodiment of the present invention, the heat treatment is performed in a closed air atmosphere.
As a further preferred aspect of the present invention, the heat treatment is carried out in a sealed reaction vessel.
Compared with the prior art, the technical scheme of the invention optimizes the preparation conditions, directly takes S, Se and PAN as raw materials, realizes one-step heat treatment synthesis in a closed environment (such as closed air), realizes the preparation of Se-doped sulfurized polyacrylonitrile, and has the advantages of simple preparation method, one-step heat treatment synthesis, high yield and environmental friendliness. On the other hand, the electronic conductivity and the ionic conductivity of a polyacrylonitrile Sulfide (SPAN) anode are improved through Se doping, the electrochemical reaction kinetics of the polyacrylonitrile Sulfide (SPAN) anode are improved, and the rate capability and the electrochemical cycle performance of the material under high surface loading capacity are improved; in addition, the Se-doped polyacrylonitrile sulfide anode has good compatibility with ethers, carbonate electrolytes and lithium cathodes, and the cycling stability of the lithium secondary battery is improved.
The preparation method provided by the invention is synthesized in one step by heat treatment in a closed environment, and is simple and environment-friendly. In the prior art, the existing preparation method of Se-doped sulfurized polyacrylonitrile material usually carries out heat treatment in flowing argon, and S and Se can be greatly volatilized along with the flowing argon in the heat treatment, so that excessive S simple substance is often required to be adopted in the prior art, and the argon waste gas containing volatilized S and Se substances is not beneficial to environmental protection; the one-step heat treatment adopted by the invention is carried out in a closed environment, and particularly can be carried out in a closed air atmosphere, so that the process requirement is greatly simplified, the raw material proportion does not need to require excessive sulfur, the sulfur utilization rate is high, and the environment is friendly.
The invention can preferably control the mass ratio of (S + Se) to PAN to be (1.5-3)/1 so as to ensure that the content of each functional component in the product meets the application requirement of the battery and obtain better performance effect of the battery. If (S, Se): if the proportion of PAN is too high, excessive elemental sulfur exists in the product, so that the prepared positive plate has the obvious defects of low coulomb efficiency of the first circle caused by shuttle effect and the like during discharging; (S, Se): if the proportion of PAN is too low, or the S content of the product is low, the capacity of the material is low. In addition, the invention can especially control the mass ratio of (S + Se) to PAN to be (1.65-1.85)/1, such as 1.8/1, so that the amount of S in the product is proper, and the subsequent sulfur removal step (which is often indispensable in the prior art) can be avoided.
In addition, the invention preferably controls the proportion of the mass of the elementary substance Se to the sum of the mass of the elementary substance S and the mass of the elementary substance Se to be 1-30%, can integrate the battery capacity (mainly brought by the element S) and the battery rate performance (brought by the element Se), and avoids the negative influence on the battery capacity when the element Se is doped too much and the negative influence on the battery rate performance when the element Se is doped too little. Particularly, when the mass of the Se simple substance accounts for 5-10% of the sum of the mass of the S simple substance and the Se simple substance, the effect is optimal.
Compared with the prior art for preparing Se-doped sulfurized polyacrylonitrile, the method can effectively solve the problems of complex synthesis process, low sulfur utilization rate, low yield and the like, and compared with an undoped sulfurized polyacrylonitrile SPAN material, the Se-doped sulfurized polyacrylonitrile material S correspondingly obtained by the preparation method disclosed by the invention1-xSexPAN improves the electronic conductivity and the ionic conductivity of the prepared material, improves the electrochemical reaction kinetics of the material, and improves the cycling stability of the electrode under high surface loading.
In conclusion, the preparation method is optimized, S, Se and PAN are directly used as raw materials, the raw materials are subjected to one-step heat treatment synthesis in a closed environment, particularly in closed air, and the Se-doped sulfurized polyacrylonitrile material which is the positive active material capable of being used for the high-specific-energy lithium secondary battery is prepared through a one-step method.
Drawings
FIG. 1 is a schematic view of a production process of a preparation method and a subsequent application example of Se-doped sulfurized polyacrylonitrile material.
Figure 2 is an XRD pattern of Se doped polyacrylonitrile sulfide.
FIG. 3 is a comparison of first cycle charge and discharge curves for sulfurized polyacrylonitrile and Se-doped sulfurized polyacrylonitrile.
FIG. 4 is a graph comparing rate performance of sulfurized polyacrylonitrile and Se-doped sulfurized polyacrylonitrile.
FIG. 5 is a graph comparing the cycling performance at 0.5C rate for sulfurized polyacrylonitrile and Se-doped sulfurized polyacrylonitrile.
FIG. 6 is a graph comparing the cycling performance at 1C rate for sulfurized polyacrylonitrile and Se-doped sulfurized polyacrylonitrile.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In general, the Se-doped sulfurized polyacrylonitrile material S in the present invention1-xSexThe preparation of PAN comprises the steps of directly heating Polyacrylonitrile (PAN), sulfur (S) and selenium (Se) mixed according to a certain mass ratio in a closed environment (such as a closed air atmosphere) to prepare Se-doped sulfurized polyacrylonitrile in one step; wherein the heat treatment temperature is 250-380 ℃, and the heat treatment time is 1-24 h. Specifically, the method can comprise the following steps:
1) uniformly mixing PAN, S and Se in a certain mass ratio.
2) Putting the mixed powder into a closed reaction kettle in air atmosphere, carrying out heat treatment at 250-380 ℃ for 1-24h, cooling to obtain S1-xSexA PAN material.
In the Se-doped sulfurized polyacrylonitrile material, the Se doping amount is in the range of 1-30 wt% based on the charge ratio of Se and S; preferably, in the mixture raw material of Se and S, the optimal doping ratio of Se is 5-10 wt%.
S produced1-xSexPAN can be used for preparing the Se-doped polyacrylonitrile sulfide positive plate and finally obtaining a corresponding lithium secondary battery; that is, S1-xSexPAN is an active material that can be used for a positive electrode of a lithium secondary battery.
Specifically, as shown in FIG. 1, S may be first introduced1-xSexForming slurry by using the PAN active material, coating the slurry on a current collector, and drying to form a positive electrode plate; for example, the following steps may be included:
1) mixing and dispersing a conductive agent, a binder and a dispersing agent according to a preset proportion to obtain a conductive binder;
2) mixing Se-doped polyacrylonitrile sulfide obtained by the preparation method with a conductive binder to obtain anode slurry;
3) coating the positive electrode slurry obtained in the step 2) on a positive electrode current collector, and performing cold pressing, drying and slicing to obtain a positive electrode plate.
Wherein the slurry proportion can be S1-xSexThe ratio of the mass of the PAN positive electrode active material to the sum of the mass of the conductive agent and the mass of the binder is 60-95: 40-5, and preferably 80-90: 20-10; if the content of the conductive agent and the binder is too high, the energy density of the battery is not favorably improved; if the conductive agent binder is too low, a strong acting force cannot be kept in the pole piece, which is not beneficial to preparing a high-loading positive pole piece and constructing an ion and electron conduction network. The mass ratio of the binder to the conductive agent is 1: 0.5-5, preferably 1: 1-2. S1-xSexThe single-side loading of the PAN active material is particularly not lower than 2mg/cm2. While applying the slurry, i.e. coating the surface of the current collector for subsequent formation of electricityThe thickness of the slurry of the electrode material layer may be 100 to 300 μm.
In addition, similar to the current collector known in the prior art, the current collector is selected from one of an aluminum foil current collector, a carbon-coated aluminum foil current collector and an aluminum mesh current collector; the conductive agent is one or more of acetylene black, graphene, Super P, carbon nano tubes and carbon fibers; the binder is selected from one or more of polyacrylic acids, cyclodextrin, guar gum and sodium alginate.
S can be replaced by Super P as the conductive agent and PAA as the binder1-xSexPAN powder, Super P powder, PAA powder and distilled water are subjected to ball milling to be mixed into slurry with the solid content of 10-50% (the optimal solid content of the slurry is 30%).
Based on the prepared positive electrode plate, a lithium secondary battery can be further constructed, and similar to the prior art, the lithium secondary battery can comprise a positive electrode plate, a negative electrode plate, a diaphragm arranged between the positive electrode plate and the negative electrode plate, and electrolyte; the negative electrode active material is selected from one of lithium metal negative electrode materials and other lithium-containing negative electrode materials, and the negative electrode current collector is copper foil; the diaphragm can be selected from the diaphragm materials existing in the lithium ion battery in the prior art, such as glass fiber, polyethylene, polypropylene, polyvinylidene fluoride, multilayer composite films of the glass fiber, the polyethylene, the polypropylene and the polyvinylidene fluoride; the electrolyte consists of a nonaqueous organic solvent, lithium salt and an additive; wherein the organic solvent comprises at least one of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, ethyl acetate, acid anhydride, N-methylpyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, sulfolane, dimethyl sulfoxide, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, dimethyl sulfite, tetrahydrofuran, fluorine-containing cyclic organic ester, sulfur-containing cyclic organic ester, ethylene glycol dimethyl ether and 1, 3-dioxolane; for example, the lithium salt may be LiPF6(ii) a The organic solvent is selected from ethylene carbonate, ethyl methyl carbonate, diethyl carbonate; the additive can be selected from one or more of FEC and VC.
Based on the preparation method of the present invention, the mass ratio of PAN and (S, Se) can be especially 1/1.8, and the sulfur utilization rate is high.
The following are specific examples:
example 1 (this example corresponds to SPAN without Se doping)
Preparation of sulfur active material S1 #: according to the mass ratio of 1: 1.8 weighing PAN and sublimed sulfur powder, adding a proper amount of ethanol as a dispersing agent, carrying out ball milling and mixing, drying the obtained mixture at 80 ℃, placing the dried powder in a closed reaction kettle in air atmosphere, and carrying out heat treatment at 300 ℃ for 500min to obtain black powder, namely the vulcanized polyacrylonitrile composite SPAN material.
Preparation of positive plate P1 #: collecting 800mg SPAN, 100mg conductive agent (Super P) and 2500mg PAA (4 wt% PAA/H)2O solution), homogenizing, coating with a scraper with a thickness of 300 μm, vacuum drying at 60 deg.C, cutting into wafer with diameter of 10mm, and vacuum drying at 80 deg.C for 4 hr to obtain single side loading of 6mg/cm2A vulcanized polyacrylonitrile composite SPAN positive plate.
Preparation of lithium secondary battery C1 #: in the glove box, a polypropylene film (phi 19mm) with the thickness of 12 mu m is used as a diaphragm, and an SPAN positive plate, the diaphragm and a metal lithium negative plate are sequentially placed, so that the diaphragm is positioned between the positive plate and the negative plate to play a role in isolation. Electrolyte injection 1.0M LiPF6in EC/DMC/EMC (1:1:1 vol%) + 5% FEC, and assembled into CR2030 button cell, and left stand for 10 h.
Example 2 (this example corresponds to Se-doped SPAN)
Preparation of sulfur active material S2 #: taking 0.96g of Se, 13.44g S and 8g of PAN, adding a proper amount of ethanol as a dispersing agent, carrying out ball milling and mixing, drying the obtained mixture at 80 ℃, placing the dried powder in a closed reaction kettle in air atmosphere, and carrying out heat treatment at 300 ℃ for 500min to obtain black powder, namely Se-doped polyacrylonitrile sulfide composite material S1-xSexA PAN material.
Preparation of positive plate P2 #: collecting 800mg SPAN, 100mg conductive agent (Super P) and 2500mg PAA (4 wt% PAA/H)2O solution), homogenizing, spreading with a 300 μm doctor blade, vacuum drying at 60 deg.C, and cutting into straight piecesThe round piece with the diameter of phi 10mm is dried for 4 hours under the vacuum condition of 80 ℃, and the loading capacity of the single surface is 6mg/cm2Se-doped sulfurized polyacrylonitrile composite material S1-xSexAnd (4) a PAN positive plate.
Preparation of lithium secondary battery C2 #: in a glove box, a polypropylene film (phi 19mm) having a thickness of 12 μm was used as a separator, and S was added1-xSexThe PAN positive plate, the diaphragm and the metal lithium negative plate are sequentially placed, so that the diaphragm is positioned between the positive plate and the negative plate to play a role in isolation. Electrolyte injection 1.0M LiPF6in EC/DMC/EMC (1:1:1 vol%) + 5% FEC, and assembled into CR2030 button cell, and left stand for 10 h.
Example 3
Preparation of sulfur active material S3 #: the procedure was the same as described in example 2, except that the mass ratio of Se: S was changed from 1:14 to 1: 2.5.
Preparation of positive plate P3 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C3 #: the procedure was the same as described in example 2.
Example 4
Preparation of sulfur active material S4 #: the procedure was the same as described in example 2, except that the mass ratio of Se: S was changed from 1:14 to 1: 9.
Preparation of positive plate P4 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C4 #: the procedure was the same as described in example 2.
Example 5
Preparation of sulfur active material S5 #: the procedure was the same as described in example 2, except that the mass ratio of Se: S was changed from 1:14 to 1: 99.
Preparation of positive plate P5 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C5 #: the procedure was the same as described in example 2.
Example 6
Preparation of sulfur active material S6 #: the procedure was as described in example 2, except that the heat treatment temperature was 380 ℃ and the heat treatment time was 1 hour.
Preparation of positive plate P6 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C6 #: the procedure was the same as described in example 2.
Example 7
Preparation of sulfur active material S7 #: the procedure was as described in example 2, except that the heat treatment temperature was 250 ℃ and the heat treatment time was 24 hours.
Preparation of positive plate P7 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C7 #: the procedure was the same as described in example 2.
Example 8
Preparation of sulfur active material S8 #: the procedure was the same as described in example 2.
Preparation of positive plate P8 #: the same procedure as described in example 2 was followed except that the conductive agent Super P in the conductive adhesive was replaced with Super P and 10 wt% CNT, and the positive electrode sheet was designated as P8 #.
Preparation of lithium secondary battery C8 #: the procedure was the same as described in example 2.
Example 9
Preparation of sulfur active material S9 #: the procedure was the same as described in example 2.
Preparation of positive plate P9 #: the preparation method is the same as that of the positive plate in the embodiment 2.
Preparation of lithium secondary battery C9 #: the procedure as described in example 2 is followed, except that the electrolyte is replaced with 1.0M LiPF6 in EC/DMC/EMC(1:1:1vol％)+10％FEC。
Example 10
Preparation of sulfur active material S10 #: the procedure was the same as described in example 2.
Preparation of positive plate P10 #: the preparation method of the positive plate is the same as that of the positive plate in example 2, except that the binder PAA in the conductive binder is replaced by PAA and CMC (PAA: CMC is 8:1), and the positive plate is marked as P10#.
Preparation of lithium secondary battery C10 #: the procedure was the same as described in example 2.
In addition, the volume of the reaction kettle can be flexibly adjusted according to the amount of the mixture raw material, for example, the filling amount of the raw material powder in the reaction kettle can be controlled to be 50 vol% to 90 vol% similarly to the conventional treatment. In addition to the sealed air atmosphere used in the above-mentioned heat treatment, other sealed environments may be used for the heat treatment, such as a sealed argon atmosphere.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (2)

1. A preparation method of Se-doped sulfurized polyacrylonitrile material is characterized in that Polyacrylonitrile (PAN) is mixed with a simple substance S and a simple substance Se to form a mixture, and a sealed reaction kettle is used for carrying out heat treatment in a closed air environment, so that the Se-doped sulfurized polyacrylonitrile material is prepared in one step without an additional desulphurization step; wherein the heat treatment temperature is 250-380 ℃, and the heat treatment time is 1-24 h; in the mixture, the mass ratio of the polyacrylonitrile PAN to the sum of the S simple substance and the Se simple substance satisfies 1/(1.65-1.85), and the mass of the Se simple substance accounts for 1% -30% of the sum of the S simple substance and the Se simple substance.
2. The method according to claim 1, wherein the mixture contains elemental Se in an amount of 5 to 10% by mass based on the sum of elemental S and elemental Se.
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